Silver halide photographic light-sensitive material

ABSTRACT

A silver halide photographic light-sensitive material is disclosed, including at least one silver halide emulsion layer, wherein the silver halide grain contained in the emulsion layer is silver chloroiodide or silver chloroiodobromide having a silver chloride content of 90 mol % or more and a silver iodide content of 0.01 to 1.0 mol %, at least one hexacyano complex is doped in an amount of at least 1×10 −7  mol % based on the total silver amount, and the emulsion layer contains a methine dye represented by the formula (I) as defined.

FIELD OF THE INVENTION

The present invention relates to a silver halide photographiclight-sensitive material for photographing, more specifically, thepresent invention relates to improvements in the stability of alight-sensitive material comprising silver chloroiodide or silverchloroiodobromide grains having a high silver chloride content.

BACKGROUND OF THE INVENTION

For the purpose of attaining simple and rapid development processing,various techniques using so-called high silver chloride grains having ahigh silver chloride content (a grain having a silver chloride contentof 90% or more and hereinafter referred to as a “high silver chloridegrain”) have been proposed. The use of high silver chloride grain isadvantageous in that the development speed increases and at the sametime, reusability of the processing solution increases. From thesereasons, the light-sensitive material for printing, such as colorprinting paper, is predominated by the type using high silver chloridegrains.

On the other hand, the emulsion for use in the printing material isdemanded to have high sensitivity and low fogging. JP-A-8-234345 (theterm “JP-A” as used herein means an “unexamined published Japanesepatent application”) discloses a technique of incorporating a slightamount of silver iodide into a high silver chloride grain, which iseffective for obtaining high sensitivity. Furthermore, U.S. Pat. No.5,268,264 discloses a technique for obtaining high sensitivity by dopinga hexacyano complex which is considered to provide a shallow electrontrap. The elevation in sensitivity considered ascribable to the shallowelectron trap is observed also when a hexacyano complex is doped into asilver chloride emulsion. However, accompanying the introduction ofsilver iodide and the doping of a hexacyano complex, fogging increasesand a technique for reducing the fogging is demanded. Furthermore,severe pressure fogging is liable to occur by the introduction of silveriodide and the doping of a hexacyano complex. The term “pressurefogging” as used herein means a phenomenon such that a developmentcenter is formed due to pressure or rubbing applied to the surface of alight-sensitive material by a transportation roller or the like duringthe processing such as exposure or development, and a color irrelevantto the image is formed.

In the present application, a time period (dry to dry) from theinitiation of processing (contact with a developer) to the completion ofdrying is defined as the processing time. In the processing of a colorprint material, a color processing time of 180 seconds is predominatingat present, however, more reduction in the processing time is demanded.Accompanying the reduction in the processing time, the transportationspeed of equipment increases and thereby the pressure to alight-sensitive material also increases. Furthermore, in order to copewith the rapid processing, the developer must have a high temperatureand a high concentration, namely, a highly active developer isnecessary, and this causes ready occurrence of pressure fogging.Accordingly, a technique of reducing the pressure fogging is demanded.

For reducing the pressure fogging, a method of introducing a defect intothe inside is known, however, this technique requires to use iodide in ahigh concentration and raises a problem of development inhibition.Furthermore, the internal defect is difficult to control and moreover,reduces the surface sensitivity or sometimes causes pressuredesensitization (a phenomenon such that the sensitivity decreases due toa pressure). On the other hand, a low concentration iodide is often usedon the grain surface so as to strengthen the adsorption of sensitizingdyes, however, the low concentration iodide is known to increase thepressure fogging and improvements on this point is also demanded.

JP-A-7-140581 discloses a method of reducing the pressure fogging usinga specific dye. The sensitizing dye for use in the present invention isdisclosed in Japanese Patent (registered) No. 2791499 andJP-A-2000-63690, where, however, the introduction of iodide is notreferred to as an essential matter and particularly, in the latter,silver chloride is disclosed as a preferred embodiment. As such, thesepublications by no means suggest the present invention.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a high silver chloridephotographic light-sensitive material having high sensitivity andreduced in fogging.

The object of the present invention has been attained by the followingmeans.

1. A silver halide photographic light-sensitive material comprising atleast one silver halide emulsion layer, wherein the silver halide graincontained in the emulsion layer is silver chloroiodide or silverchloroiodobromide having a silver chloride content of 90 mol % or moreand a silver iodide content of 0.01 to 1.0 mol %, at least one hexacyanocomplex is doped in an amount of at least 1×10⁻⁷ mol % based on thetotal silver amount, and the emulsion layer contains a methine dyerepresented by the following formula (I):

wherein Y represents an atomic group necessary for forming aheterocyclic ring or an atomic group necessary for forming a benzenering condensed with a heterocyclic ring, which may further be condensedwith another carbon ring or heterocyclic ring or may have a substituent,Z¹ and Z² each represents a single bond or an atomic group necessary forforming a nitrogen-containing heterocyclic ring which may further becondensed with another carbon ring or heterocyclic ring or may have asubstituent, R represents an alkyl group, an aryl group or aheterocyclic group, D represents a group necessary for forming a methinedye, L¹ and L² each represents a methine group, p represents 0 or 1, Mrepresents a counter ion, and m represents a number of 0 or morenecessary for neutralizing the electric charge within the molecule.

2. The silver halide photographic light-sensitive material as describedin 1, wherein in formula (I), Y represents an atomic group necessary forforming a pyrrole ring, a furan ring, a thiophene ring or a benzene ringcondensed with a pyrrole ring, a furan ring or a thiophene ring, and thering formed by Y may be condensed with another carbon ring orheterocyclic ring or may have a substituent.

3. The silver halide photographic light-sensitive material as describedin 1, wherein the formula (I) is selected from the following formula(II):

wherein Y¹¹ represents an atomic group necessary for forming a pyrrolering, a furan ring or a thiophene ring, or an atomic group necessary forforming an indole ring, a benzofuran ring or a benzothiophene ring,which may further be condensed with another carbon ring or heterocyclicring or may have a substituent, X¹¹ represents an oxygen atom, a sulfuratom, a selenium atom or NR¹³, R¹¹, R¹² and R¹³ each represents an alkylgroup, an aryl group or a heterocyclic group, Z¹¹ represents an atomicgroup necessary for forming a nitrogen-containing heterocyclic ringwhich may further be condensed with another carbon ring or heterocyclicring or may have a substituent, L¹¹, L¹², L¹³, L¹⁴ and L¹⁵ eachrepresents a methine group, p1 represents 0 or 1, n1 represents 0, 1, 2,3 or 4, M¹ represents a counter ion and m1 represents a number of 0 ormore necessary for neutralizing the electric charge within the molecule.

4. The silver halide photographic light-sensitive material as describedin 1, wherein the formula (I) is selected from the following formula(III):

wherein Y²¹ represents an atomic group necessary for forming a pyrrolering, a furan ring or a thiophene ring, which may further be condensedwith another carbon ring or heterocyclic ring or may have a substituent,X²¹ and X²² each represents an oxygen atom, a sulfur atom, a seleniumatom or NR²³, R²¹, R²² and R²³ each represents an alkyl group, an arylgroup or a heterocyclic group, V²¹, V²², V²³ and V²⁴ each represents ahydrogen atom or a substituent, provided that two adjacent substituentsare not combined with each other to form a saturated or unsaturatedcondensed ring, L²¹, L²² and L²³ each represents a methine group, n2represents 0, 1, 2, 3 or 4, M² represents a counter ion and m2represents a number of 0 or more necessary for neutralizing the electriccharge within the molecule.

5. The silver halide photographic light-sensitive material as describedin any one of 1 to 4, wherein the silver halide grain is doped with atleast one Ir complex.

6. The silver halide light-sensitive material as described in any one of1 to 5, wherein silver halide grains occupying 50% or more of the entiregrain volume have a high silver bromide localized phase having a silverbromide content 10 mol % or more higher than that of the adjacent phaseand the high silver bromide localized phase contains at least one Ircomplex.

7. A method for forming an image, comprising imagewise exposing anddeveloping a silver halide photographic light-sensitive materialcomprising a support having thereon at least one silver halide emulsionlayer, wherein the silver halide light-sensitive material is thelight-sensitive material described in 1 to 6 and the total processingtime of the light-sensitive material is 75 seconds or less.

8. The method for forming an image as described in 7, wherein digitalscanning exposure is performed.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is described in detail below.

In the present invention, specific spectral sensitizing dyes are used.The dyes are described below.

In the present invention, when a specific moiety is called “a group”,this means that the moiety itself may not be substituted or may besubstituted by one or more (to the possible maximum number of)substituents. For example, “an alkyl group” means a substituted orunsubstituted alkyl group. The substituent which can be used in thecompounds for use in the present invention includes any substituent,irrespective of the presence or absence of substitution.

Assuming that the substituent is V, the substituent represented by V isnot particularly limited, however, examples thereof include a halogenatom, an alkyl group [(including a cycloalkyl group and a bicycloalkylgroup), also including an alkenyl group (including a cycloalkenyl group,a bicycloalkenyl group and a tricycloalkenyl group) and an alkynylgroup], an aryl group, a heterocyclic group, a cyano group, a hydroxygroup, a nitro group, a carboxyl group, an alkoxy group, an aryloxygroup, a silyloxy group, a heterocyclic oxy group, an acyloxy group, acarbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxygroup, an amino group (including an anilino group), an ammonio group, anacylamino group, an aminocarbonylamino group, an alkoxycarbonylaminogroup, an aryloxy-carbonylamino group, a sulfamoylamino group, analkylsulfonylamino group, an arylsulfonylamino group, a mercapto group,an alkylthio group, an arylthio group, a heterocyclic thio group, asulfamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinylgroup, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, analkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, anarylazo group, a heterocyclic azo group, an imido group, a phosphinogroup, a phosphinyl group, a phosphinyloxy group, a phosphinylaminogroup, a phospho group, a silyl group, a hydrazino group, a ureido groupand other known substituents.

More specifically, examples of V include a halogen atom (e.g., fluorine,chlorine, bromine, iodine), an alkyl group [a linear, branched orcyclic, substituted or unsubstituted alkyl group; the alkyl groupincludes an alkyl group (preferably an alkyl group having from 1 to 30carbon atoms, e.g., methyl, ethyl, n-propyl, isopropyl, tert-butyl,n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), acycloalkyl group (preferably a substituted or unsubstituted cycloalkylgroup having from 3 to 30 carbon atoms, e.g., cyclohexyl, cyclopentyl,4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substitutedor unsubstituted bicycloalkyl group having from 5 to 30 carbon atoms,e.g., bicyclo[1.2.2]heptan-2-yl, bicyclo[2.2.2]octan-3-yl), and atricyclo-alkyl group having many ring structures; the alkyl group in thesubstituents described below (for example, the alkyl group in analkylthio group) includes an alkyl group having such a concept andfurther includes an alkenyl group, a cycloalkenyl group, abicycloalkenyl group and an alkynyl group, which are described below],an alkenyl group [a linear, branched or cyclic, substituted orunsubstituted alkenyl group; the alkenyl group includes an alkenyl group(preferably a substituted or unsubstituted alkenyl group having from 2to 30 carbon atoms, e.g., vinyl, allyl, prenyl, geranyl, oleyl), acycloalkenyl group (preferably a substituted or unsubstitutedcycloalkenyl group having from 3 to 30 carbon atoms, e.g.,2-cyclopenten-1-yl, 2-cyclohexen-1-yl) and a bicycloalkenyl group (asubstituted or unsubstituted bicycloalkenyl group having, preferably asubstituted or unsubstituted bicycloalkenyl group having from 5 to 30carbon atoms, e.g., bicyclo[2.2.1]hept-2-en-1-yl,bicyclo[2.2.2]oct-2-en-4-yl)], an alkynyl group (preferably asubstituted or unsubstituted alkynyl group having from 2 to 30 carbonatoms, e.g., ethynyl, propargyl, trimethylsilylethynyl), an aryl group(preferably a substituted or unsubstituted aryl group having from 6 to30 carbon atoms, e.g., phenyl, p-tolyl, naphthyl, m-chlorophenyl,o-hexadecanoylaminophenyl), a heterocyclic group (preferably amonovalent group resulting from eliminating one hydrogen atom from a 5-or 6-membered, substituted or unsubstituted, aromatic or non-aromaticheterocyclic compound, more preferably a 5- or 6-membered aromaticheterocyclic group having from 3 to 30 carbon atoms, e.g., 2-furyl,2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl; a cationic heterocyclicgroup such as 1-methyl-2-pyridinio and 1-methyl-2-quinolinio may also beused), a cyano group, a hydroxyl group, a nitro group, a carboxyl group,an alkoxy group (preferably a substituted or unsubstituted alkoxy grouphaving from 1 to 30 carbon atoms, e.g., methoxy, ethoxy, isopropoxy,tert-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferablya substituted or unsubstituted aryloxy group having from 6 to 30 carbonatoms, e.g., phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy,3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group(preferably a silyloxy group having from 3 to 20 carbon atoms, eg.,trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group(preferably a substituted or unsubstituted heterocyclic oxy group havingfrom 2 to 30 carbon atoms, e.g., 1-phenyltetrazol-5-oxy,2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group,a substituted or unsubstituted alkylcarbonyloxy group having from 2 to30 carbon atoms and a substituted or unsubstituted aryl-carbonyloxygroup having from 6 to 30 carbon atoms, e.g., formyloxy, acetyloxy,pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), acarbamoyloxy group (preferably a substituted or unsubstitutedcarbamoyloxy group having from 1 to 30 carbon atoms, e.g.,N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy,morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy,N-n-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably asubstituted or unsubstituted alkoxycarbonyloxy group having from 2 to 30carbon atoms, e.g., methoxycarbonyloxy, ethoxycarbonyloxy,tert-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group(preferably a substituted or unsubstituted aryloxycarbonyloxy grouphaving from 7 to 30 carbon atoms, e.g., phenoxycarbonyloxy,p-methoxyphenoxycarbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy), anamino group (preferably an amino group, a substituted or unsubstitutedalkylamino group having from 1 to 30 carbon atoms and a substituted orunsubstituted anilino group having from 6 to 30 carbon atoms, e.g.,amino, methylamino, dimethylamino, anilino, N-methylanilino,diphenylamino), an ammonio group (preferably an ammonio group, anammonio group substituted by a substituted or unsubstituted alkyl, arylor heterocyclic group having from 1 to 30 carbon atoms, e.g.,trimethylammonio, triethylammonio, diphenylmethylammonio), an acylaminogroup (preferably a formylamino group, a substituted or unsubstitutedalkylcarbonylamino group having from 1 to 30 carbon atoms and asubstituted or unsubstituted arylcarbonylamino group having from 6 to 30carbon atoms, e.g., formylamino, acetylamino, pivaloylamino,lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), anaminocarbonylamino group (preferably a substituted or unsubstitutedaminocarbonylamino group having from 1 to 30 carbon atoms, e.g.,carbamoylamino, N,N-dimethylaminocarbonylamino,N,N-diethylaminocarbonylamino, morpholinocarbonylamino), analkoxycarbonylamino group (preferably a substituted or unsubstitutedalkoxycarbonylamino group having from 2 to 30 carbon atoms, e.g.,methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino,n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino), anaryloxycarbonylamino group (preferably a substituted or unsubstitutedaryloxycarbonylamino group having from 7 to 30 carbon atoms, e.g.,phenoxycarbonylamino, p-chlorophenoxycarbonylamino,m-(n-octyloxyphenoxycarbonylamino)), a sulfamoylamino group (preferablya substituted or unsubstituted sulfamoylamino group having from 0 to 30carbon atoms, e.g., sulfamoylamino, N,N-dimethylaminosulfonylamino,N-n-octylaminosulfonylamino), an alkyl- or aryl-sulfonylamino group(preferably a substituted or unsubstituted alkylsulfonylamino grouphaving from 1 to 30 carbon atoms and a substituted or unsubstitutedarylsulfonylamino group having from 6 to 30 carbon atoms, e.g.,methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino,2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), amercapto group, an alkylthio group (preferably a substituted orunsubstituted alkylthio group having from 1 to 30 carbon atoms, e.g.,methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably asubstituted or unsubstituted arylthio group having from 6 to 30 carbonatoms, e.g., phenylthio, p-chlorophenylthio, m-methoxyphenylthio), aheterocyclic thio group (preferably a substituted or unsubstitutedheterocyclic thio group having from 2 to 30 carbon atoms, e.g.,2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group(preferably a substituted or unsubstituted sulfamoyl group having from 0to 30 carbon atoms, e.g., N-ethylsulfamoyl,N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl,N-acetylsulfamoyl, N-benzoylsulfamoyl, N-(N′-phenylcarbamoyl)sulfamoyl),a sulfo group, an alkyl- or aryl-sulfinyl group (preferably asubstituted or unsubstituted alkylsulfinyl group having from 1 to 30carbon atoms and a substituted or unsubstituted arylsulfinyl grouphaving from 6 to 30 carbon atoms, e.g., methylsulfinyl, ethylsulfinyl,phenylsulfinyl, p-methylphenylsulfinyl), an alkyl- or aryl-sulfonylgroup (preferably a substituted or unsubstituted alkylsulfonyl grouphaving from 1 to 30 carbon atoms and a substituted or unsubstitutedarylsulfonyl group having from 6 to 30 carbon atoms, e.g.,methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl),an acyl group (preferably a formyl group, a substituted or unsubstitutedalkylcarbonyl group having from 2 to 30 carbon atoms, a substituted orunsubstituted arylcarbonyl group having from 7 to 30 carbon atoms and asubstituted or unsubstituted heterocyclic carbonyl group having from 4to 30 carbon atoms in which the carbonyl group is bonded through acarbon atoms, e.g., acetyl, pivaloyl, 2- chloroacetyl, stearoyl,benzoyl, p-n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl,2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted orunsubstituted aryloxycarbonyl group having from 7 to 30 carbon atoms,e.g., phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl,p-t-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably asubstituted or unsubstituted alkoxycarbonyl group having from 2 to 30carbon atoms, e.g., methoxycarbonyl, ethoxycarbonyl,tert-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group(preferably a substituted or unsubstituted carbamoyl group having from 1to 30 carbon atoms, e.g., carbamoyl, N-methylcarbamoyl,N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl,N-(methylsulfonyl)carbamoyl), an aryl- or heterocyclic-azo group(preferably a substituted or unsubstituted arylazo group having from 6to 30 carbon atoms and a substituted or unsubstituted heterocyclic azogroup having from 3 to 30 carbon atoms, e.g., phenylazo,p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group(preferably N-succinimide and N-phthalimide), a phosphino group(preferably a substituted or unsubstituted phosphino group having from 2to 30 carbon atoms, e.g., dimethylphosphino, diphenylphosphino,methylphenoxyphosphino), a phosphinyl group (preferably a substituted orunsubstituted phosphinyl group having from 2 to 30 carbon atoms, e.g.,phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxygroup (preferably a substituted or unsubstituted phosphinyloxy grouphaving from 2 to 30 carbon atoms, e.g., diphenoxyphosphinyloxy,dioctyloxyphosphinyloxy), a phosphinylamino group (preferably asubstituted or unsubstituted phosphinylamino group having from 2 to 30carbon atoms, e.g., dimethoxyphosphinylamino,dimethylaminophosphinylamino), a phospho group, a silyl group(preferably a substituted or unsubstituted silyl group having from 3 to30 carbon atoms, e.g., trimethylsilyl, tert-butyldimethylsilyl,phenyldimethylsilyl), a hydrazino group (preferably a substituted orunsubstituted hydrazino group having from 0 to 30 carbon atoms, e.g.,trimethylhydrazino) and a ureido group (preferably a substituted orunsubstituted ureido group having from 0 to 30 carbon atoms, e.g.,N,N-dimethylureido).

Also, two V may combine to have a structure condensed with a ring (anaromatic or non-aromatic, hydrocarbon or heterocyclic ring; these ringsmay further be combined to form a polycyclic condensed ring; examplesthereof include a benzene ring, a naphthalene ring, an anthracene ring,a quinoline ring, a phenanthrene ring, a fluorene ring, a triphenylenering, a naphthacene ring, a biphenyl ring, a pyrrole ring, a furan ring,a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, apyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, anindolizine ring, an indole ring, a benzofuran ring, a benzothiophenering, an isobenzofuran ring, a quinolizine ring, a quinoline ring, aphthalazine ring, a naphthylizine ring, a quinoxaline ring, aquinoxazoline ring, a quinoline ring, a carbazole ring, a phenanthridinering, an acridine ring, a phenanthroline ring, a thianthrene ring, achromene ring, a xanthene ring, a phenoxathiine ring, a phenothiazinering and a phenazine ring).

Among these substituents V, those having a hydrogen atom may further besubstituted by the above-described substituent after eliminating thehydrogen atom. Examples of such a composite substituent include anacylsulfamoyl group, an alkylsulfonylcarbamoyl group and anarylsulfonylcarbamoyl group. Specific examples thereof includemethylsulfonylcarbamoyl, p-methylphenylsulfonylcarbamoyl,acetylsulfamoyl and benzoylsulfamoyl.

The methine dye represented by formula (I) for use in the presentinvention is described in detail below.

When Y is an atomic group necessary for forming a heterocyclic ring,examples of the 5-membered unsaturated heterocyclic ring formed by Yinclude a pyrrole ring, a pyrazole ring, an imidazole ring, a triazolering, a furan ring, an oxazole ring, an isooxazole ring, a thiophenering, a thiazole ring, an isothiazole ring, a thiadiazole ring, aselenophene ring, a selenazole ring, an isoselenazole ring, atellurophene ring, a tellurazole ring, an isotellurazole ring. Examplesof the 6-membered unsaturated heterocyclic ring include a pyridine ring,a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrane ring anda thiopyrane ring. The ring formed by Y may further be condensed withanother 5- or 6-membered carbon ring or heterocyclic ring to form, forexample, an indole ring, a benzofurane ring, a benzothiophene ring or athienothiophene ring. Also, the ring formed by Y may be an unsaturatedheterocyclic ring resulting from the hydrogenation of a part of doublebonds in the above-described heterocyclic rings, such as pyrroline ring,pyrazoline ring, imidazoline ring, dihydrofuran ring, oxazoline ring,dihydrothiophene ring and thiazoline ring, or a saturated heterocyclicring resulting from the hydrogenation of all double bonds, such aspyrrolidine ring, pyrazolidine ring, imidazolidine ring,tetrahydrofurane ring, oxazolidine ring, tetrahydrothiophene ring andthiazolidine ring.

When Y is an atomic group necessary for forming a benzene ring condensedwith a heterocyclic ring, examples of the ring formed by Y include anindole ring, a benzofuran ring and a benzothiophene ring.

The ring formed by Y is preferably a pyrrole ring, a furan ring, athiophene ring, an indole ring, a benzofuran ring or a benzothiophenering, more preferably a pyrrole ring, a thiophene ring or a furan ring.

The nitrogen-containing heterocyclic ring formed by Z¹ and Z² ispreferably a 5- or 6-membered nitrogen-containing heterocyclic ring andexamples thereof include an oxazole ring, a thiazole ring, a selenazolering, an imidazole ring, a 2-pyridine ring, a 4-pyridine ring and a3,3-dimethyl-3H-pyrrole ring. Other than the ring formed by Y, a carbonring such as benzene ring, cyclohexene ring and naphthalene ring, or aheterocyclic ring such as furan ring and thiophene ring, may becondensed thereto.

The nitrogen-containing heterocyclic ring formed by Z¹ and Z² is morepreferably an oxazole ring, a thiazole ring, an imidazole ring or a2-pyridine ring, more preferably an oxazole ring or a thiazole ring.

The ring formed by Y and the nitrogen-containing heterocyclic ringformed by Z¹ and Z² each may have a substituent and examples thereofinclude those described above as the substituent represented by V.

Among the substituents V, preferred are the above-described alkyl group,aryl group, aromatic heterocyclic group, alkoxy group, alkylthio group,cyano group and halogen atom.

The alkyl group represented by R may be unsubstituted or unsubstitutedand includes an unsubstituted alkyl group having from 1 to 18,preferably 1 to 7, more preferably from 1 to 4, carbon atoms (e.g.,methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl,dodecyl, octadecyl), and a substituted alkyl group having from 1 to 8,preferably from 1 to 7, more preferably from 1 to 4, carbon atoms{examples of the substituent include the above-described substituentsrepresented by V (such as an aryl group, an unsaturated hydrocarbongroup, a carboxy group, a sulfo group, a sulfate group, a cyano group, ahalogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxygroup, a mercapto group, an alkoxy group, an aryloxy group, an alkylthiogroup, an arylthio group, an acyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoylgroup, a heterocyclic group, an alkylsulfonylcarbamoyl group, anacylcarbamoyl group, an acylsulfamoyol group and analkylsulfonylsulfamoyl group, which may further be substituted)}.

The aryl group represented by R may be unsubstituted or substituted andincludes an unsubstituted aryl group having from 6 to 20, preferably 6to 15, more preferably from 6 to 10, carbon atoms (e.g., phenyl,1-naphthyl) and a substituted aryl group having from 6 to 26, preferablyfrom 6 to 21, more preferably from 6 to 16, carbon atoms {examples ofthe substituent include the above-described substituents represented byV (such as an alkyl group, an aryl group, an unsaturated hydrocarbongroup, a carboxy group, a sulfo group, a sulfate group, a cyano group, ahalogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxygroup, a mercapto group, an alkoxy group, an aryloxy group, an alkylthiogroup, an arylthio group, an acyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoylgroup, a heterocyclic group, an alkylsulfonylcarbamoyl group, anacylcarbamoyl group, an acylsulfamoyl group and analkylsulfonylsulfamoyl group, which may further be substituted)}.

The heterocyclic group represented by R may be unsubstituted orsubstituted and includes an unsubstituted heterocyclic group having from1 to 20, preferably from 1 to 15, more preferably from 1 to 10, carbonatoms (e.g., pyrrole, furan, thiophene) and a substituted heterocyclicgroup having from 1 to 26, preferably from 1 to 21, more preferably from1 to 16, carbon atoms {examples of the substituent include theabove-described substituents represented by V}.

R is preferably a group substituted by an acid group or a group having adissociative proton {specifically, a carboxyl group, a sulfo group, aphosphonic acid group, a boronic acid group, —CONHSO₂—, —SO₂NHSO₂—,—CONHCO—, —SO₂NHCO—}, more preferably an alkyl group substituted by theabove-described acid group or group having a dissociative proton, stillmore preferably a substituted alkyl group containing any one of acarboxyl group, a sulfo group, an alkylsulfonylcarbamoyl group (e.g.,methanesulfonylcarbonyl), an acylcarbamoyl group (e.g.,acetylcarbamoyl), an acylsulfamoyl group (e.g., acetylsulfamoyl) and analkylsulfonylsulfamoyl group (e.g., methanesulfonylsulfamoyl), and mostpreferably a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropylgroup, a 3-sulfobutyl group, a 4-sulfobutyl group or amethanesulfonylcarbamoylmethyl group.

The methine group represented by L¹ and L² may have a substituent andexamples of the substituent include the above-described substituentsrepresented by V.

p is preferably 0.

M is included in formula (I) so as to show the presence of cation oranion when required for neutralizing the ion charge of the dye. Whethera certain dye is cation or anion or bears a net ion charge depends onthe substituent and the environment (e.g., pH) in a solution. Typicalexamples of the cation include inorganic cation such as hydrogen ion(H⁺), alkali metal ion (e.g., sodium ion, potassium ion, lithium ion)and alkaline earth metal ion (e.g., calcium ion), and organic ion suchas ammonium ion (e.g., ammonium ion, tetraalkylammonium ion,triethylammonium ion, pyridinium ion, ethylpyridinium ion,1,8-diazabicyclo[5.4.0]-7-undecenium ion). The anion may be eitherinorganic anion or organic anion and examples thereof include halideanion (e.g., fluoride ion, chloride ion, bromide ion, iodide ion),substituted arylsulfonate ion (e.g., p-toluenesulfonate ion,p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g.,1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion,2,6-naphthalenedisulfonate ion), alkylsulfate ion (e.g., methylsulfateion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborateion, picrate ion, acetate ion and trifluoromethanesulfonate ion. Also,an ionic polymer or another dye having a charge opposite the dye may beused.

The cation is preferably sodium ion, potassium ion, triethylammoniumion, tetraethylammonium ion, pyridinium ion, ethylpyridinium ion ormethylpyridinium ion, and the anion is preferably perchlorate ion,iodide ion, bromide ion or substituted arylsulfonate ion (e.g.,p-toluenesulfonate ion).

m represents a number of 0 or more necessary for balancing the electriccharge, preferably a number of 0 to 4. m is 0 when an inner salt isformed.

D is a group necessary for forming a methine dye and any methine dye maybe formed by D, however, the methine dye is preferably a cyanine dye, amerocyanine dye, a rhodacyanine dye, a trinuclear merocyanine dye, atetranuclear merocyanine dye, an allopolar dye, a hemicyanine dye or astyryl dye. These dyes are described in detail in F. M. Harmer,Heterocyclic Compounds—Cyanine Dyes and Related Compounds, John Wiley &Sons, New York, London (1964), D. M. Sturmer, HeterocyclicCompounds—Special topics in heterocyclic chemistry, Chap. 18, Section14, pp. 482-515.

Examples of the formulae of preferred dyes include the formulaedescribed U.S. Pat. No. 5,994,051, pages 32 to 36, and the formulaedescribed in U.S. Pat. No. 5,747,236, pages 30 to 34. For cyanine dyes,merocyanine dyes and rhodacyanine dyes, formulae (XI), (XII) and (XIII)described in U.S. Pat. No. 5,340,694, columns 21 to 22, are preferred(on the condition that the numbers of n12, n15, n17 and n18 are notlimited and each is an integer of 0 or more (preferably 4 or less)).Among these, cyanine, merocyanine and rhodacyanine dyes are preferred,and a cyanine dye is more preferred.

In the case where a cyanine dye is formed by D in formula (I), thecyanine dye can also be expressed by the following resonance formula(I′):

Preferred examples of the compound represented by formula (I) are morespecifically set forth below. The compound represented by formula (I) ismore preferably selected from the following formulae (a) to (1).

wherein D, R, M and m have the same meanings as those in formula (I), X¹represents an oxygen atom, a sulfur atom, a selenium atom or NR¹(wherein R¹ represents an alkyl group, an aryl group or a heterocyclicgroup), and X² represents an oxygen atom, a sulfur atom or NR² (whereinR² represents a hydrogen atom, an alkyl group, an aryl group or aheterocyclic group). The benzene ring or heterocyclic ring in theformulae may further be substituted by the above-described substituentrepresented by V or may be condensed with another carbon ring orheterocyclic ring.

Among these formulae, preferred are formulae (a) to (i), more preferredare formulae (a) to (f), still more preferred are formulae (a) to (c),and particularly preferred are formulae (a) and (c).

The methine dye represented by formula (I) is more preferably a methinedye selected from the following formulae (IA), (IB), (IC) and (ID):

wherein Y, R, Z¹, Z², L¹, L² and p have the same meanings as in formula(I), L³¹, L³², L³³, L³⁴ and L³⁵ each represents a methine group, p3represents 0 or 1, n3 represents 0, 1, 2, 3 or 4, Y³¹ represents anatomic group necessary for forming a 5- or 6-memberednitrogen-containing heterocyclic ring, which may be condensed withanother carbon ring or heterocyclic ring or may have a substituent, M³represents a counter ion, m3 represents a number of 0 to 4 necessary forneutralizing the electric charge of the molecular, and R³¹ represents asubstituted or unsubstituted alkyl, aryl or heterocyclic group;

wherein Y, R, Z¹, Z², L¹, L² and p have the same meanings as in formula(I), L⁴¹ and L⁴² each represents a methine group, n4 represents 0, 1, 2,3 or 4, Y⁴¹ represents an atomic group necessary for forming an acidicnucleus, which may be condensed with another carbon ring or heterocyclicring or may have a substituent, M⁴ represents a counter ion, and m4represents a number of 0 or more necessary for neutralizing the electriccharge of the molecule;

wherein Y, R, Z¹, Z², L¹, L² and p have the same meanings as in formula(I), L⁵¹, L⁵², L⁵³, L⁵⁴, L⁵⁵, L⁵⁶ and L⁵⁷ each represents a methinegroup, p5 represents 0 or 1, n51 and n52 each represents 0, 1, 2, 3 or4, Y⁵¹ and Y⁵² each represents an atomic group necessary for forming a5- or 6-membered nitrogen-containing heterocyclic ring, which may have asubstituent, provided that Y⁵² may further be condensed with anothercarbon ring or heterocyclic ring, M⁵ represents a counter ion, m5represents a number of 0 to 4 necessary for neutralizing the electriccharge of the molecule, and R⁵¹ and R⁵² each represents a substituted orunsubstituted alkyl, aryl or heterocyclic group;

wherein Y, R, Z¹, Z², L¹, L² and p have the same meanings as in formula(I), L⁶¹, L⁶², L⁶³, L⁶⁴, L⁶⁵, L⁶⁶ and L⁶⁷ each represents a methinegroup, p6 represents 0 or 1, n61 and n62 each represents 0, 1, 2, 3 or4, Y⁶¹ and Y⁶² each represents an atomic group necessary for forming a5- or 6-membered nitrogen-containing heterocyclic ring which may have asubstituent, provided that Y⁶² may further be condensed with anothercarbon ring or heterocyclic ring, M⁶ represents a counter ion, m6represents a number of 0 to 4 necessary for neutralizing the electriccharge of the molecular, and R⁶¹ and R⁶² each represents a substitutedor unsubstituted alkyl, aryl or heterocyclic group.

In formulae (IA), (IB), (IC) and (ID), the 5- or 6-memberednitrogen-containing heterocyclic ring represented by Y³¹, Y⁵² and Y⁶²may further be condensed with another 5- or 6-membered carbon ring orheterocyclic ring. Examples of the carbon ring include a benzene ringand a naphthalene ring, and examples of the heterocyclic ring include afuran ring and a thiophene ring. The ring condensed is preferably acarbon ring, more preferably a benzene ring. Specifically, a 5- or6-membered nitrogen-containing heterocyclic ring (type) described lateras an example of Z¹¹ in formula (II) is preferred and specific examplesthereof include those described as examples of Z₁₁, Z₁₂, Z₁₃, Z₁₄ andZ₁₆ in U.S. Pat. No. 5,340,694, columns 23 and 24.

Y⁴¹ represents an atomic group necessary for forming an acyclic orcyclic acidic nucleus, and any acidic nucleus form of generalmerocyanine dyes may be formed. In a preferred form, a thiocarbonylgroup or a carbonyl group is present next to the position where themethine chain of Y⁴¹ is connected.

The “acidic nucleus” as used herein is defined, for example, in T. H.James (compiler), The Theory of the Photographic Process, 4th ed., page198, MacMillan Publishing (1977). Specific examples thereof includethose described in U.S. Pat. Nos. 3,567,719, 3,575,869, 3,804,634,3,837,862, 4,002,480 and 4,925,777, and JP-A-3-167546.

The acidic nucleus preferably forms a 5- or 6-memberednitrogen-containing heterocyclic ring comprising carbon, nitrogen andchalcogen (typically oxygen, sulfur, selenium and tellurium) atoms andexamples thereof include the following nuclei:

nuclei of 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one,hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidin-4-one,2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, isooxazolin-5-one,2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodanine,thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione,thiophen-3-one, thiophen-3-one-1,1-dioxide, indolin-2-one,indolin-3-one, 2-oxoindazolinium, 3-oxoindazolinium,5,7-dioxo-6,7-dihydrothiazolo[3,2-a]pyrimidine, cyclohexane-1,3-dione,3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid,2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one,pyrido[1,2-a]pyrimidine-1,3-dione, pyrazolo[1,5-b]quinazolone,pyrazolo[1,5-a]benzimidazole, pyrazolopyridone,1,2,3,4-tetrahydroquinoline-2,4-dione,3-oxo-2,3-dihydrobenzo[d]thiophene-1,1-dioxide and3-dicyanomethylene-2,3-dihydrobenzo[d]thiophene-1,1-dioxide; and nucleihaving an exomethylene structure where the carbonyl or thiocarbonylgroup constituting the above-described nuclei is substituted at theactive methylene position of an active methylene compound having astructure such as ketomethylene or cyanomethylene.

The acidic nucleus formed by Y⁴¹ is preferably hydantoin, 2- or4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazolin-2,4-dione,thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dione, barbituricacid or 2-thiobarbituric acid, more preferably hydantoin, 2- or4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid or2-thiobarbituric acid, still more preferably 2- or 4-thiohydantoin,2-oxazolin-5-one, rhodanine or barbituric acid.

The 5- or 6-membered nitrogen-containing heterocyclic ring formed by Y⁵¹and Y⁶¹ is resultant from eliminating an oxo or thioxo group from theheterocyclic ring represented by Y⁴¹, preferably resultant fromeliminating an oxo or thioxo group from hydantoin, 2- or4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazolin-2,4-dione,thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituricacid or 2-thiobarbituric acid, more preferably resultant fromeliminating an oxo or thioxo group from hydantoin, 2- or4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid or2-thiobarbituric acid, still more preferably resultant from eliminatingan oxo or thioxo group from 2- or 4-thiohydantoin, 2-oxazolin-5-one orrhodanine.

R³¹, R⁵¹, R⁵², R⁶¹, R⁶² and the substituent (if there, R⁴¹ is allottedthereto) on a nitrogen atom of the acidic nucleus Y⁴¹each represents asubstituted or unsubstituted alkyl, aryl or heterocyclic group andpreferred examples thereof include those described above as examples forR in the methine dye of formula (I).

Among those, R³¹, R⁴¹, R⁵¹, R⁵², R⁶¹ and R⁶² each is preferably asubstituted or unsubstituted alkyl group, more preferably an alkyl groupsubstituted by an acid group or a group having a dissociative proton,still more preferably a substituted alkyl group containing any one of acarboxyl group, a sulfo group, —CONHSO₂—, —SO₂NHSO₂—, —CONHCO— and—SO₂NHCO—, particularly preferably a carboxymethyl group, a 2-sulfoethylgroup, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl groupor a methanesulfonylcarbamoylmethyl group.

L³¹, L³², L³³, L³⁴, L³⁵, L⁴¹, L⁴², L⁵¹, L⁵², L⁵³, L⁵⁴, L⁵⁵, L⁵⁶, L⁵⁷,L⁶¹, L⁶², L⁶³, L⁶⁴, L⁶⁵, L⁶⁶ and L⁶⁷ each independently represents amethine group. These methine groups each may have a substituent andexamples of the substituent include the above-described substituentsrepresented by V.

This methine group may form a ring with another methine group or mayform a ring together with Y³¹, Y⁴¹, Y⁵¹, Y⁵², Y⁶¹ and Y⁶².

L¹, L², L³⁴, L³⁵, L⁵⁶, L⁶⁶ and L⁶⁷ each is preferably an unsubstitutedmethine group.

n3, n4, n51, n52, n61 and n62 each represents 0, 1, 2, 3 or 4 and wheneach is 2 or more, the methine group is repeated but those methinegroups may not be the same. n3, n4, n51 and n62 each is preferably 0, 1,2 or 3, more preferably 0, 1 or 2, still more preferably 0 or 1. n52 andn61 each is preferably 0 or 1, more preferably 0.

p3, p5 and p6 each independently represents 0 or 1, preferably 0.

M³, M⁴, M⁵ and M⁶ each represents a counter ion and preferred examplesthereof include those described above for M. m3, m4, m5 and m6 eachrepresents a number of 0 or more, preferably from 0 to 4, necessary forneutralizing the electric charge within the molecule and when an innersalt is formed, m3, m4, m5 and m6 each is 0.

Among formulae (IA), (IB), (IC) and (ID), the methine dye represented byformula (I) is preferably a cyanine dye (IA). The cyanine dye (IA) ismore preferably represented by formula (II).

The dye represented by formula (II) is described in detail below.

In formula (II), Y¹¹ represents an atomic group necessary for forming apyrrole ring, a furan ring or a thiophene ring or an atomic groupnecessary for forming an indole ring, a benzofuran ring or abenzotiophene ring, which may be condensed with another carbon ring orheterocyclic ring or may have a substituent, however, which ispreferably not condensed with another ring. The ring formed by Y¹¹ispreferably a pyrrole ring, a furan ring or a thiophene ring.

X¹¹ represents an oxygen atom, a sulfur atom, a selenium atom or NR¹³,preferably an oxygen atom, a sulfur atom or NR¹³, more preferably anoxygen atom or a sulfur atom.

The nitrogen-containing heterocyclic ring formed by Z¹¹ may be condensedwith a carbon ring such as benzene ring, cyclohexene ring or naphthalenering, or a heterocyclic ring such as furan ring or thiophene ring. Thering condensed is preferably a carbon ring, more preferably a benzenering.

The nitrogen-containing heterocyclic ring formed by Z¹¹ is preferably athiazoline ring, a thiazole ring, a benzothiazole ring, an oxazolinering, an oxazole ring, a benzoxazole ring, a selenazoline ring, aselenazole ring, a benzoselenazole ring, a tellurazoline ring, atellurazole ring, a benzotellurazole ring, a 3,3-dialkylindolenine ring(e.g., 3,3-dimethylindolenine), an imidazoline ring, an imidazole ring,a benzimidazole ring, an isooxazole ring, an isothiazole ring, apyrazole ring, a 2-pyridine ring, a 4-pyridine ring, a 2-quinoline ring,a 4-quinoline ring, a 1-isoquinoline ring, a 3-isoquinoline ring, animidazo[4,5-b]quinoxaline ring, an oxadiazole ring, a thiadiazole ring,a tetrazole ring, a pyrimidine ring or a ring resultant from condensinga benzene ring to the above-described rings.

Among these, preferred are a benzoxazole ring, a benzothiazole ring, abenzimidazole ring and a quinoline ring, more preferred are abenzoxazole ring and a benzothiazole ring. These rings each may besubstituted by the above-described substituent represented by V.Specific examples of the nitrogen-containing heterocyclic ring formed byZ¹¹include those described as examples of Z₁₁, Z₁₂, Z₁₃, Z₁₄ and Z₁₆ inU.S. Pat. No. 5,340,694, columns 23 and 24.

Examples of the alkyl group, the aryl group and the heterocyclic grouprepresented by R¹¹, R¹² and R¹³ include the groups described for R inthe methine dye of formula (I). R¹¹ and R¹² each is preferably an alkylgroup substituted by an acid group or a group having a dissociativeproton, more preferably a substituted alkyl group containing any one ofa carboxyl group, a sulfo group, —CONHSO₂—, —SO₂NHSO₂—, —CONHCO— and—SO₂NHCO—, still more preferably a 2-sulfoethyl group, a 3-sulfopropylgroup, a 3-sulfobutyl group, a 4-sulfobutyl group, a carboxymethyl groupor a methanesulfonylcarbamoylmethyl group.

R¹³ is preferably an unsubstituted alkyl group, more preferably a methylgroup or an ethyl group.

The methine group represented by L¹¹, L¹², L¹³, L¹⁴ and L¹⁵ may beunsubstituted or substituted and examples of the substituent include theabove-described substituents represented by V.

L¹⁴ and L¹⁵ each is preferably an unsubstituted methine group.

n1 represents 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably0, 1 or 2, still more preferably 0 or 1, and when n1 is 2 or more, themethine group is repeated but those methine groups may not be the same.

p1 represents 0 or 1, preferably 0.

Examples of M¹ include those described above as the ion for M in themethine dye of formula (I). M¹ is preferably cation and preferredexamples of the cation include sodium, potassium, triethylammonium,pyridinium and N-ethylpyridinium.

m1 represents a number of 0 or more necessary for neutralizing theelectric charge within the molecule, preferably 0, 1, 2 or 3, and whenan inner salt is formed, m1 is 0.

The methine dye represented by formula (II) is preferably represented byformula (III).

The dye represented by formula (III) is described in detail below.

In formula (III), the ring formed by Y²¹ is selected from a pyrrolering, a furan ring and a thiophene ring.

The ring formed by Y²¹ may be condensed in any direction but, taking athiophene ring as an example, out of the thieno[3,2-d]azole type wherethe sulfur atom of the thiophene ring is present in the same side as X²¹with respect to the condensed carbon-carbon bond (the type of formula(c)), the thieno[2,3-d]azole type where the sulfur atom of the thiophenering is present in the opposite side to X²¹ (the type of formula (a))and the thieno[3,4-d]azole type where the another ring is condensed at3-position and 4-position of the thiophene ring (the type of formula(b)), the former two types are preferred. In the case where the dye isrequired to have spectral absorption in the long wavelength region as asensitizing dye, the type of formula (a) is more preferred.

The ring formed by Y²¹ preferably has a substituent on the ring andexamples of the substituent include the above-described substituentsrepresented by V. The substituent is preferably an alkyl group (e.g.,methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group(e.g., 1-pyrrolyl), an alkoxy group (e.g., methoxy), an alkylthio group(e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine,chlorine, bromine, iodine), more preferably a chlorine atom or a bromineatom.

X²¹ and X²² each represents an oxygen atom, a sulfur atom, a seleniumatom or NR²³, preferably an oxygen atom, a sulfur atom or NR²³, morepreferably an oxygen atom or a sulfur atom, still more preferably asulfur atom.

Examples of the alkyl group, the aryl group and the heterocyclic grouprepresented by R²¹, R²² and R²³ include the groups described above for Rin the methine dye of formula (I). R²¹ and R²² each is preferably analkyl group substituted by an acid group or a group having adissociative proton, more preferably a substituted alkyl groupcontaining any one of a carboxyl group, a sulfo group, —CONHSO₂—,—SO₂NHSO₂—, —CONHCO— and —SO₂NHCO—, still more preferably a 2-sulfoethylgroup, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutylgroup, a carboxymethyl group or a methanesulfonylcarbamoylmethyl group.Furthermore preferably, either one of R²¹ and R²² is a 2-sulfoethylgroup, a 3-sulfopropyl group, a 3-sulfobutyl group or a 4-sulfobutylgroup and another one is a carboxymethyl group or amethanesulfonylcarbamoylmethyl group.

R²³ is preferably an unsubstituted alkyl group, more preferably a methylgroup or an ethyl group.

Examples of the substituents represented by V²¹, V²², V²³ and V²⁴include the above-described substituents represented by V, however, twoadjacent substituents are not combined with each other to form anunsaturated condensed ring. V²¹ and V²⁴ each is preferably a hydrogenatom and V²² and V²³ each is preferably a hydrogen atom, an alkyl group(e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclicgroup (e.g., 1-pyrrolyl), an alkoxy group (e.g., methoxy), an alkylthiogroup (e.g., methylthio), a cyano group or a halogen atom (e.g.,fluorine, chlorine, bromine, iodine). V²³ is more preferably a hydrogenatom and V²² is more preferably a halogen atom, still more preferably achlorine atom or a bromine atom.

The methine group represented by L²¹, L²² and L²³ may be unsubstitutedor substituted and examples of the substituent include theabove-described substituents represented by V.

n2 represents 0, 1, 2, 3 or 4 and when n2 is 2 or more, the methinegroup is repeated but those methine groups may not be the same. n2 ispreferably 0, 1, 2 or 3, more preferably 0, 1 or 2, still morepreferably 0 or 1.

When n2 is 0, L²¹ is preferably an unsubstituted methine group and whenn2 is 1, L²² is preferably a methine group substituted by anunsubstituted alkyl group, more preferably a methyl-substituted methinegroup or an ethyl-substituted methine group, and L²¹ and L²³ each ispreferably an unsubstituted methine group.

Examples of M² include the ions described above for M in the methine dyeof formula (I). M² is preferably cation and preferred examples thereofinclude sodium, potassium, triethylammonium, pyridinium andN-ethylpyridium.

m² represents a number of 0 or more necessary for neutralizing theelectric charge within the molecule, preferably 0, 1, 2 or 3, and whenan inner salt is formed, m² is 0.

Preferred embodiments of the compound of formula (I) for use in thesilver halide emulsion of the present invention are described in moredetail below.

In the case of using this compound in a red-sensitive emulsion layer,the compound of formula (I) is preferably represented by formula (III)where one of X²¹ and X²² is an oxygen atom and another is a sulfur atom;Y²¹ is a pyrrole, furan or thiophene ring substituted by a halogen atom;R²¹ and R²² each is a sulfoalkyl group, a carboxyalkyl group or analkylsulfonylcarbamoylalkyl group; n2 is 1; L²¹ and L²³ each is anunsubstituted methine group; L²² is a methyl-substituted methine groupor an ethyl-substituted methine group; V²¹, V²³ and V²⁴ each is ahydrogen atom; V²² is an alkyl group (e.g., methyl), an alkoxy group(e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group ora halogen atom (e.g., fluorine, chlorine, bromine, iodine), morepreferably a halogen atom; M² is an organic or inorganic monovalentcation; and m2 is 0 or 1.

In the case of using this compound in a green-sensitive emulsion layer,the compound of formula (I) is preferably represented by formula (III)where X²¹ and X²² both are an oxygen atom; Y²¹ is a pyrrole, furan orthiophene ring substituted by a chlorine atom or a bromine atom; R²¹ andR²² each is a sulfoalkyl group, a carboxyalkyl group or analkylsulfonylcarbamoylalkyl group; n2 is 1; L²¹ and L²³ each is anunsubstituted methine group; L²² is a methyl-substituted methine groupor an ethyl-substituted methine group; V²¹, V²³ and V²⁴ each is ahydrogen atom; V²² is an alkyl group (e.g., methyl), an aryl group(e.g., phenyl), an aromatic heterocyclic group (e.g., 2-thienyl), analkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), acyano group or a halogen atom (e.g., fluorine, chlorine, bromine,iodine), more preferably a halogen atom; M² is an organic or inorganicmonovalent cation; and m2 is 0 or 1.

In the case of using this compound in a blue-sensitive emulsion layer,the compound of formula (I) is preferably represented by formula (III)where X²¹ and X²² both are a sulfur atom; Y²¹ is a thiophene ringsubstituted by a halogen atom; R²¹ and R²² each is a sulfoalkyl group, acarboxyalkyl group or an alkylsulfonylcarbamoylalkyl group; n2 is 0; L²¹is an unsubstituted methine group; V²¹, V²³ and V²⁴ each is a hydrogenatom, V²² is an alkyl group (e.g., methyl), an alkoxy group (e.g.,methoxy), an alkylthio group (e.g., methylthio), a cyano group or ahalogen atom (e.g., fluorine, chlorine, bromine, iodine), morepreferably a halogen atom, still more preferably a chlorine atom or abromine atom; M² is an organic or inorganic monovalent cation; and m2 is0 or 1.

Specific examples of the compound represented by formula (I) (includingthe compounds represented by formulae (II) and (III) as lower concepts)of the present invention are set forth below, however, the presentinvention is not limited thereto.

Other than those shown below, the compound may also be selected fromMethine Dyes S-1 to S-95 described in Japanese Patent Application No.2000-124612.

The compound represented by formula (I) (including the compounds oflower concepts) of the present invention can be synthesized by themethods described in F. M. Harmer, Heterocyclic Compounds—Cyanine Dyesand Related Compounds, John Wiley & Sons, New York, London (1964), D. M.Sturmer, Heterocyclic Compounds—Special topics in heterocyclicchemistry, Chap. 18, Sec. 14, pp. 482-515, John Wiley & Sons, New York,London (1977), and Rodd's Chemistry of Carbon Compounds, 2nd ed., Vol.IV, Part B, Chap. 15, pp. 369-422, Elsevier Science Publishing CompanyInc., New York (1977).

The compounds represented by formula (I) of the present invention may beused in combination of two or more thereof.

Also, the compound of formula (I) for use in the present invention maybe used in combination with another sensitizing dye other than thecompound of the present invention, within the same emulsion. The dyeused in combination is preferably a cyanine dye, a merocyanine dye, arhodacyanine dye, a trinuclear merocyanine dye, a tetranuclearmerocyanine dye, an allopolar dye, a hemicyanine dye or a styryl dye,more preferably a cyanine dye, a merocyanine dye or a rhodacyanine dye,still more preferably a cyanine dye. These dyes are described in detailin F. M. Harmer, Heterocyclic Compounds—Cyanine Dye and RelatedCompounds, John Wiley & Sons, New York, London (1964), D. M. Sturmer,Heterocyclic Compounds—Special topics in heterocyclic chemistry, Chap.18, Section 14, pp. 482-515.

Examples of preferred dyes include the sensitizing dyes represented bythe formulae or set forth as specific examples in U.S. Pat. No.5,994,051, pp. 32-44, and U.S. Pat. No. 5,747,236, pp. 30-39.

For cyanine dyes, merocyanine dyes and rhodacyanine dyes, formulae (XI),(XII) and (XIII) described in U.S. Pat. No. 5,340,694, columns 21 and22, are preferred (on the condition that the numbers of n₁₂, n₁₅, n₁₇and n₁₈ are not limited and each is an integer of 0 or more (preferably4 or less)).

These sensitizing dyes, which can be used in combination with thecompound of formula (I), may be used individually or in combination oftwo or more thereof and when two or more dyes are used, a combination ofproviding supersensitization effect is preferred. Typical examplesthereof include those described in U.S. Pat. Nos. 2,688,545, 2,977,229,3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480,3,672,898, 3,679,428, 3,303,377, 3,769,301, 3,814,609, 3,837,862 and4,026,707, British Patents 1,344,281 and 1,507,803, JP-B-43-49336 (theterm “JP-B” as used herein means an “examined Japanese patentpublication”) and JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.

Together with the sensitizing dye, a dye which itself has no spectralsensitization effect or a substance which absorbs substantially novisible light, but which exhibits supersensitization may be contained inthe emulsion.

Examples of the supersensitizer (for example, pyrimidylamino compounds,triazinylamino compounds, azolium compounds, aminostyryl compounds,aromatic organic formaldehyde condensates, azaindene compounds, cadmiumsalts) useful in the spectral sensitization of the present invention andexamples of the combination of a supersensitizer with a sensitizing dyeare described in U.S. Pat. Nos. 3,511,664, 3,615,613, 3,615,632,3,615,641, 4,596,767, 4,945,038, 4,965,182, 2,933,390, 3,635,721,3,743,510, 3,617,295 and 3,635,721. With respect to the use methodthereof, those described in these patents are also preferred.

The silver halide photographic emulsion and the silver halidephotographic light-sensitive material according to the present inventionare described in detail below.

The methine dye (the same applies to other sensitizing dye orsupersensitizer) of formula (I) for use in the present invention may beadded to the silver halide emulsion according to the present inventionin any step heretofore recognized as useful during the preparation ofthe emulsion. The methine dye may be added at any time or in any step aslong as it is before the coating of the emulsion, for example, duringthe formation and/or in the period before the desalting of silver halidegrains, during the desalting and/or in the period from the desaltinguntil the initiation of chemical ripening as disclosed in U.S. Pat. Nos.2,735,766, 3,628,960, 4,183,756 and 4,225,666, JP-A-58-184142 andJP-A-60-196749, immediately before or during the chemical ripening, orin the period from the chemical ripening until the coating as disclosedin JP-A-58-113920. Also, as disclosed in U.S. Pat. No. 4,225,666 andJP-A-58-7629, the same compound by itself or in combination with acompound having a foreign structure may be added in parts, for example,one part during the grain formation and another part during the chemicalripening or after the completion of chemical ripening, or one partbefore or during the chemical ripening and another part after thecompletion of chemical ripening. When added in parts, the kind of thecompound or the combination of compounds may be varied.

The amount added of the methine dye (the same applies to othersensitizing dye or supersensitizer) for use in the present inventionvaries depending on the shape and size of silver halide grain, however,the methine dye can be used in an amount of 1×10⁻⁶ to 8×10⁻³ mol per molof silver halide. For example, when the silver halide grain size is from0.2 to 1.3 μm, the amount added is preferably from 2×10⁻⁶ to 3.5×10⁻³,more preferably from 7.5×10⁻⁶ to 1.5×10⁻³ mol, per mol of silver halide.

The methine dye (the same applies to other sensitizing dye orsupersensitizer) for use in the present invention can be disperseddirectly in the emulsion or can be added to the emulsion in the form ofa solution after dissolving the dye in an appropriate solvent such asmethyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water orpyridine or in a mixed solvent thereof. At this time, additives such asa base, an acid or a surfactant can be allowed to be present together.For dissolving the dye, an ultrasonic wave may also be used. In addingthe compound, a method of dissolving the compound in a volatile organicsolvent, dispersing the solution in a hydrophilic colloid and adding thedispersion to the emulsion described in U.S. Pat. No. 3,469,987, amethod of dispersing the compound in a water-soluble solvent and addingthe dispersion to the emulsion described in JP-B-46-24185, a method ofdissolving the compound in a surfactant and adding the solution to theemulsion described in U.S. Pat. No. 3,822,135, a method of dissolvingthe compound using a compound capable of red shifting and adding thesolution to the emulsion described in JP-A-51-74624, and a method ofdissolving the compound in an acid substantially free of water andadding the solution to the emulsion described in JP-A-50-80826 may beused. For the addition to the emulsion, the methods described in U.S.Pat. Nos. 2,912,343, 3,342,605, 2,996,287 and 3,429,835 may also beused.

Examples of the organic solvent which dissolves the methine dye for usein the present invention include methyl alcohol, ethyl alcohol,n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, benzylalcohol, fluoroalcohol, methyl cellosolve, acetone, pyridine and a mixedsolvent thereof.

In dissolving the methine dye for use in the present invention in water,an organic solvent described above or a mixed solvent thereof, a base ispreferably added. The base may be either an organic salt or an organicbase and examples thereof include amine derivatives (e.g.,triethylamine, triethanolamine), pyridine derivatives, sodium hydroxide,potassium hydroxide, sodium acetate and potassium acetate. The methinedye is preferably dissolved by the method of adding the dye to a mixedsolvent of water and methanol and further adding thereto triethylamineequimolar to the dye.

The silver halide emulsion for use in the present invention is describedbelow. The silver halide grain is preferably a cubic or tetradecahedralcrystal grain having substantially {100} faces (the grain may haverounded corners and may have a hk1 plane) or an octahedral crystalgrain. Alternatively, 50% or more of the entire projected area arepreferably occupied by tabular crystal grains comprising a {100} face ora {111} face and having an aspect ratio of 2 or more. The aspect ratiois a value obtained by dividing the diameter of a circle correspondingto the projected area of a grain by the thickness of the grain.

The silver halide emulsion for use in the present invention is a silverchloroiodide or silver chloroiodobromide emulsion and in view of rapidprocessability, preferably a silver chloroiodide or silverchloroiodobromide emulsion having a silver chloride content of 95 mol %or more, more preferably a silver chloroiodide or silverchlorobromoiodide emulsion having a silver chloride content of 98 mol %or more.

The grain for use in the present invention preferably comprises a corepart and a shell part (outermost layer) having a larger iodide contentthan the core part. In the core part, 90% or more thereof preferablycomprises silver chloride. The core part may comprise two or moremoieties different in the halogen composition. The silver iodide contentof the core part is preferably 0.5 mol % or less, more preferably 0.1mol % of less, per mol of the total silver.

The shell part preferably occupies 50% or less, more preferably 20% orless, in the entire volume of a grain. The shell part preferably has asilver iodochloride phase in a proportion of 0.1 to 1.0 mol %, morepreferably from 0.2 to 0.60 mol %, per mol of the total silver, wherebyhigh sensitivity and excellent suitability for high-intensity exposurecan be advantageously attained. However, the position where iodide ionis introduced is restricted from the standpoint of obtaining ahigh-sensitivity and low-fogging emulsion. As the iodide ion isintroduced more inside an emulsion grain, the elevation of sensitivityis smaller. Therefore, an iodide salt solution is preferably added tothe region outside 50% of the grain volume, more preferably outside 70%,most preferably outside 80%. At the same time, the addition of theiodide salt solution is preferably finished inside 98% of the grainvolume, most preferably inside 96%. By finishing the addition of theiodide salt solution slightly inside the grain surface, the obtainedemulsion can have higher sensitivity and lower fogging.

The iodide ion may be introduced by adding an iodide salt solutionsolely or by adding an iodide salt solution together with the additionof a silver salt solution and a high chloride salt solution. In thelatter case, the iodide salt solution and the high chloride solution maybe added separately or a mixed solution of iodide salt and high chloridesalt may be added. The iodide salt is added in the form of a solublesalt such as alkali or alkaline earth iodide salt. The iodide may alsobe introduced by cleaving iodide ion from an organic molecule asdescribed in U.S. Pat. No. 5,389,508. Also, fine silver iodide grain maybe used as another iodide ion source.

The iodide salt solution may be added concentrically at a certain periodin the grain formation or may be added over a certain period of time.

The distribution of iodide ion concentration in the depth directioninside a grain can be measured by an etching/TOF-SIMS (Time ofFlight-Secondary Ion Mass Spectrometry) method using, for example,TRIFTII-type TOF-SIMS manufactured by Phi Evans. The TOF-SIMS method isspecifically described in Hyomen Bunseki Gijutsu Sensho Niji IonShituryou Bunseki Ho (Surface Analysis Technology Selection, SecondaryIon Mass Spectrometry), compiled by Nippon Hyomen Kagaku Kai, issued byMaruzen (1999). When emulsion grains are analyzed by theetching/TOF-SIMS method, the analysis may show that even if the additionof iodide salt solution is finished inside a grain, the iodide ion isbleeding out toward the grain surface. In the case where the emulsion ofthe present invention contains silver iodide, it is preferably shown inthe analysis by the etching/TOF-SIMS method that the iodide ion has aconcentration maximum on the grain surface and the iodide ionconcentration is attenuated toward the inside.

In the silver halide grain for use in the present invention, ahexacyano-complex is doped. The center metal which forms a complex withcyan ion may be a metal described in U.S. Pat. No. 5,518,871 but ispreferably iron or ruthenium. The hexacyano-complex can be doped at anystage during the grain formation but is preferably doped into the areainside 3% or more of the grain volume. The hexacyano-complex is added inan amount of 1×10⁻⁷ mol or more per mol of silver during the grainformation, but is preferably added in an amount of 1×10⁻⁷ to 1×10⁻² mol,most preferably from 1×10⁻⁶ to 5×10⁻⁴ mol.

In the present invention, an iridium complex is preferably doped. Theligand is preferably fluoride ion, chloride ion, bromide ion or iodideion, more preferably chloride ion or bromide ion. Also, a so-calledorganic compound described in U.S. Pat. Nos. 5,360,712, 5,457,021 and5,462,849 may also be coordinated as the ligand. It is also preferred tocoordinate H₂O as the ligand. Specific preferred examples of the iridiumcomplex include [IrCl₆]³⁻, [IrCl₆]²⁻, [IrCl₅(H₂O)]²⁻, [IrCl₅(H₂O)]⁻,[IrCl₄(H₂O)₂]⁻, [IrCl₄(H₂O)₂]⁰, [IrCl₃(H₂O)₃]⁰, [IrCl₃(H₂O)₃]⁺,[IrBr₆]³⁻, [IrBr₆]²⁻, [IrBr₅(H₂O)]²⁻, [IrBr₅(H₂O)]⁻, [IrBr₄(H₂O)₂]⁻,[IrBr₄(H₂O)₂]⁰, [IrBr₃(H₂O)₃]⁰ and [IrBr₃(H₂O)₃]⁺. This iridium complexis preferably added during the grain formation in an amount of 1×10⁻¹⁰to 1×10⁻³ mol, most preferably from 1×10⁻⁸ to 1×10⁻⁵ mol, per mol ofsilver.

In the case where the emulsion of the present invention contains asilver bromide localized phase, a silver bromide localized phase havinga silver bromide content of at least 10 mol % different from theneighborhood is preferably formed on the grain surface. The silverbromide content of the silver bromide localized phase is preferably from10 to 60 mol %, most preferably from 20 to 50 mol %. The silver bromidelocalized phase is preferably constituted by from 0.1 to 5 mol % ofsilver, more preferably from 0.3 to 4 mol % of silver, based on thetotal amount of silver constituting the silver halide grain for use inthe present invention. The silver bromide localized phase preferablycontains Ir-complex ion such as iridium(III) chloride, iridium(III)bromide, iridium(IV) chloride, sodium hexachloroiridium(III), potassiumhexachloroiridium(IV), hexaammineiridium(IV) salt,trioxalatoiridium(III) salt and trioxalatoiridium(IV) salt. The amountadded of this compound varies over a wide range according to the purposebut is preferably from 10⁻⁹ to 10⁻² mol per mol of silver halide.

In the silver halide grain for use in the present invention, ion of ametal selected from Group VIII metals in the periodic table, namely,osmium, rhodium, platinum, ruthenium, palladium, cobalt and nickel, or acomplex ion thereof may be used and these ions may be used individuallyor in combination. Furthermore, multiple kinds of metals may also beused.

The above-described metal ion-providing compound can be incorporatedinto the silver halide grain of the present invention by adding thecompound to an aqueous solution working out to a dispersion medium atthe formation of silver halide grains, such as aqueous gelatin solution,aqueous halide solution, aqueous silver salt solution or other aqueoussolution, or by previously incorporating the metal ion into a silverhalide fine grain, adding the fine grain to the silver halide emulsionand dissolving this emulsion. The metal ion may be incorporated into thegrain at any step before, during or immediately after the grainformation but the timing of addition is determined depending on to whichposition or in what amount the metal ion is incorporated into the grain.

Other than the Group VIII metals, various polyvalent metal ionimpurities can be introduced into the silver halide emulsion for use inthe present invention during the formation or physical ripening ofemulsion grains. The amount added of this compound varies over a widerange depending on the purpose but is preferably from 10⁻⁹ to 10⁻² molper mol of silver halide.

The silver halide grain contained in the silver halide emulsion for usein the present invention preferably has an average grain size (a numberaverage of grain sizes, by taking the diameter of a circle equivalent tothe projected area of a grain as the grain size) of 0.1 to 2 μm.

The grain size distribution is preferably so-called monodisperse, wherethe coefficient of variation (obtained by dividing the standarddeviation of the grain size distribution by an average grain size) ispreferably 20% or less, preferably 15% or less, more preferably 10% orless. For the purpose of obtaining a wide latitude, it is preferred toblend and use this monodisperse emulsion in the same layer or to applythe monodisperse emulsion in multiple layers.

The silver halide emulsion for use in the present invention may containvarious compounds or precursors thereof for the purpose of preventingfogging during the production, storage or photographic processing of alight-sensitive material or for stabilizing the photographicperformance. With respect to specific examples of such compounds, thosedescribed in JP-A-62-215272 supra., pages 39 to 72 are preferably used.In addition, 5-arylamino-1,2,3,4-thiatriazole compounds (the arylresidue having at least one electron-withdrawing group) described inEP04547647 are also preferably used.

For elevating storability of the silver halide emulsion, the followingcompounds are preferably used in the present invention: hydroxamic acidderivatives described in JP-A-11-109576; cyclic ketones having inadjacency to the carbonyl group a double bond with both ends beingsubstituted by an amino group or a hydroxyl group described inJP-A-11-327094 (in particular, those represented by formula (S1); theparagraphs 0036 to 0071 may be incorporated into the presentspecification by reference); sulfo-substituted catechol andhydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid,2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonicacid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonicacid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof) describedin JP-A-11-143011; and water-soluble reducing agents represented byformulae (I) to (III) of JP-A-11-102045.

The silver halide emulsion for use in the present invention is usuallysubjected to chemical sensitization. The chemical sensitization may beperformed using sulfur sensitization of adding a labile sulfur compound,noble metal sensitization represented by gold sensitization, andreduction sensitization, individually or in combination. Preferredexamples of the compounds for use in the chemical sensitization includethose described in JP-A-62-215272, page 18, right lower column to page22, right upper column. In particular, the silver halide emulsion ispreferably subjected to gold sensitization. By virtue of goldsensitization, fluctuation in the photographic performance upon scanexposure with a laser ray or the like can be more reduced.

In the gold sensitization of the silver halide emulsion for use in thepresent invention, various inorganic compounds, Au(I) complexes havingan inorganic ligand and Au(I) compounds having an organic ligand may beused. Examples of the inorganic compound include chloroauric acid andsalts thereof, and examples of the Au(I) complex having an inorganicligand include aurous dithiocyanate compounds such as potassiumaurous(I) dithiocyanate, and aurous dithiosulfate compounds such astrisodium aurous(I) dithiosulfate.

Examples of the Au(I) compound having an organic ligand, which can beused, include bis-Au(I) mesoionic heterocycles such asbis(1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) Au(I) tetrafluoroboratedescribed in JP-A-4-267249, organic mercapto Au(I) complexes such aspotassium bis(1-[3-(2-sulfonatobenzamide)phenyl]-5-mercaptotetrazolepotassium salt) aurate(I) pentahydrate described in JP-A-11-218870, andAu(I) compounds coordinated with nitrogen compound anion such asbis(1-methylhydantoinato) Au(I) sodium salt tetrahydrate described inJP-A-4-268550. In addition, Au(I) thiolate compounds described in U.S.Pat. No. 3,503,749, gold compounds described in JP-A-8-69074,JP-A-8-69075 and JP-A-9-269554, and compounds described in U.S. Pat.Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245 and 5,912,111 may alsobe used. The amount of such a compound added may vary over a wide rangeaccording to the case but is usually from 5×10⁻⁷ to 5×10⁻³ mol,preferably from 5×10⁻⁶ to 5×10⁻⁴ mol, per mol of silver halide.

A colloidal gold sulfide may also be used and the production methodthereof is described in Research Disclosure, No. 37154, Solid StateIonics, Vol. 79, pp. 60-66 (1995), and Compt. Rend. Hebt. Seances, Vol.263, page 1328, Acad. Sci. Sect. B (1966). The colloidal gold sulfidemay have various sizes and even those having a particle size of 50 nm orless may be used. The amount added thereof may vary over a wide rangedepending on the case but is usually, in terms of gold atom, from 5×10⁻⁷to 5×10⁻³ mol, preferably from 5×10⁻⁶ to 5×10⁻⁴ mol, per mol of silverhalide.

In the present invention, the gold sensitization may be combined withanother sensitization such as sulfur sensitization, seleniumsensitization, tellurium sensitization, reduction sensitization or noblemetal sensitization using a compound other than gold compounds.

In the silver halide photographic light-sensitive material of thepresent invention, conventionally known photographic materials andadditives may be used.

For example, the photographic support which can be used includes atransmission-type support and a reflection-type support. Examples of thetransmission-type support which can be preferably used includetransparent film such as cellulose nitrate film and polyethyleneterephthalate, and polyester of 2,6-naphthalenedicarboxylic acid (NDCA)and ethylene glycol (EG) or polyester of NDCA, terephthalic acid and EG,having provided thereon an information recording layer such as magneticlayer. The reflection-type support is particularly preferably areflective support having laminated thereon a plurality of polyethylenelayers or polyester layers and containing a white pigment such astitanium oxide in at least one of these water-resistant resin layers(laminated layers).

The reflective support for use in the present invention is morepreferably a reflective support obtained by providing a polyolefin layerhaving fine holes on a paper substrate in the side where a silver halideemulsion layer is provided. The polyolefin layer may comprise multiplelayers and in this case, it is preferred that the polyolefin layer (forexample, polypropylene, polyethylene) adjacent to the gelatin layer inthe silver halide emulsion layer side has no fine hole and thepolyolefin layer (for example, polypropylene, polyethylene) in the sidecloser to the paper substrate is formed of polyolefin having fine holes.The density of the polyolefin layer having a multilayer structure or asingle layer structure interposed between the paper substrate and aphotographic constituent layer is preferably from 0.40 to 1.0 g/ml, morepreferably from 0.50 to 0.70 g/ml. The thickness of the polyolefin layerhaving a multilayer structure or a single layer structure interposedbetween the paper substrate and a photographic constituent layer ispreferably from 10 to 100 μm, more preferably from 15 to 70 μm. Theratio of the thickness of the polyolefin layer to the thickness of thepaper substrate is preferably from 0.05 to 0.5, more preferably from 0.1to 0.2.

On the surface opposite the photographic constituent layer (backsurface) of the paper support, a polyolefin layer is preferably providedso as to enhance the rigidity of the reflective support. In this case,the polyolefin layer on the back surface is preferably formed ofpolyethylene or polypropylene having a matted surface, preferablypolypropylene. The thickness of the polyolefin layer on the back surfaceis preferably from 5 to 50 μm, more preferably from 10 to 30 μm, and thedensity thereof is preferably from 0.7 to 1.1 g/ml. Examples of thepreferred embodiment of the polyolefin layer provided on the papersubstrate of the reflective support for use in the present inventioninclude those described in JP-A-10-333277, JP-A-10-333278,JP-A-11-52513, JP-A-11-65024, EP0880065 and EP0880066.

The above-described water-resistant resin layer preferably contains afluorescent brightening agent. The fluorescent brightening agent mayalso be dispersed in a hydrophilic colloid layer of the light-sensitivematerial. The florescent brightening agent which can be used ispreferably a florescent brightening agent of benzoxazole type, coumarintype or pyrazoline type, more preferably a florescent brightening agentof benzoxazolyl naphthalene type or benzoxazolyl stilbene type. Theamount used thereof is not particularly limited but is preferably from 1to 100 mg/m². In the case of mixing the fluorescent brightening agent inthe water-resistant resin, the mixing ratio to the resin is preferablyfrom 0.0005 to 3% by weight, more preferably from 0.001 to 0.5% byweight.

The reflection-type support may also be a support obtained by providinga hydrophilic colloid layer containing a white pigment on thetransmission-type support or on the above-described reflection-typesupport.

The reflection-type support may also have a metal surface with mirrorreflection or secondary diffuse reflection.

The support for use in the light-sensitive material of the presentinvention may be a white polyester-base support for display or a supportin which a layer containing a white pigment is provided on the supportin the side having a silver halide emulsion layer. Furthermore, in orderto improve the sharpness, an antihalation layer is preferably providedon the support in the side where a silver halide emulsion layer iscoated or on the back surface thereof. The support is preferably set tohave a transmission density of 0.35 to 0.8 so that the display can beviewed with either reflected light or transmitted light.

For the purpose of enhancing the sharpness or the like of an image, thelight-sensitive material of the present invention preferably contains adye capable of decoloration upon processing (particularly, oxonol-basedye) described in EP-A-0337490, pp. 27-76, by adding the dye to ahydrophilic colloid layer such that the light-sensitive material has anoptical reflection density at 680 nm of 0.70 or more, or preferablycontains 12% by weight or more (more preferably 14% by weight or more)of titanium oxide surface-treated with a di-, tri- or tetra-hydricalcohol (e.g., trimethylolethane), in a water-resistant resin layer ofthe support.

For the purpose of preventing irradiation or halation or enhancing thesafelight immunity or the like, the light-sensitive material of thepresent invention preferably contains a dye capable of decoloration uponprocessing (particularly, oxonol dye or cyanine dye) described inEP-A-0337490, pp. 27-76, in a hydrophilic colloid layer. In addition,the dye described in European Patent 0819977 may also be preferably usedin the present invention.

Some of these water-soluble dyes worsen the color separation orsafelight immunity when the amount used thereof is increased. Examplesof the dye which can be used without changing the color separation forthe worse include the water-soluble dyes described in JP-A-5-127324,JP-A-5-127325 and JP-A-5-216185.

In the present invention, a colored layer capable of decoloration uponprocessing is used in place of or in combination with the water-solubledye. The colored layer capable of decoloration upon processing may beused by directly contacting it with an emulsion layer or may be disposedto contact therewith through an intermediate layer containing a processcolor mixing inhibitor such as gelatin or hydroquinone. This coloredlayer is preferably provided as an underlayer (in the support side) ofan emulsion layer which forms the primary color as the color of thecolored layer. All colored layers corresponding to respective primarycolors may be individually provided or only a part thereof may be freelyselected and provided. Also, a colored layer subjected to coloringscorresponding to a plurality of primary color regions may also beprovided. The optical reflection density of the colored layer ispreferably such that the optical density value at a wavelength having ahighest optical density in the wavelength region used for exposure (in anormal printer exposure, a visible light region of 400 to 700 nm and inthe case of scanning exposure, the wavelength of the light source usedfor the scanning exposure) is from 0.2 to 3.0, more preferably from 0.5to 2.5, still more preferably from 0.8 to 2.0.

For the formation of the colored layer, a conventionally known methodmay be used. Examples thereof include a method of incorporating a dyedescribed in JP-A-2-282244, page 3, right upper column to page 8, or adye described in JP-A-3-7931, page 3, right upper column to page 11,left lower column, which is in the form of a solid fine particledispersion, into a colloid layer, a method of mordanting an anionic dyeto a cationic polymer, a method of adsorbing a dye to a fine particlesuch as silver halide and thereby fixing the dye in a layer, and amethod of using colloidal silver described in JP-A-1-239544. Withrespect to the method of dispersing fine powder of a dye in the solidstate, a method of incorporating fine powder of a dye which issubstantially water-insoluble at least at a pH of 6 or less butsubstantially water-soluble at least at a pH of 8 or more, is described,for example, in JP-A-2-308244, pages 4 to 13. The method of mordantingan anionic dye to a cationic polymer is described, for example, inJP-A-2-84637, pages 18 to 26. Also, the preparation method of colloidalsilver as a light absorber is disclosed in U.S. Pat. Nos. 2,688,601 and3,459,563. Among these methods, the method of incorporating fine powderof a dye and a method of using colloidal silver are preferred.

The silver halide photographic light-sensitive material of the presentinvention can be used for color negative film, color positive film,color reversal film color reversal printing paper, color printing paperand the like, but is preferably used as color printing paper.

The color printing paper preferably comprises at least one yellowcolor-forming silver halide emulsion layer, at least one magentacolor-forming silver halide emulsion layer and at least one cyancolor-forming silver halide emulsion layer. In general, these silverhalide emulsion layers are provided in the order of, from the sidenearer to the support, a yellow color-forming silver halide emulsionlayer, a magenta color-forming silver halide emulsion layer and a cyancolor-forming silver halide emulsion layer.

Of course, a layer structure different from the above may be employed.

The silver halide emulsion layer containing a yellow coupler may bedisposed at any position on the support, however, when the yellowcoupler-containing layer comprises silver halide tabular grains, thelayer is preferably provided at the position more distant from thesupport than at least one layer of the magenta coupler-containing silverhalide emulsion layer and the cyan coupler-containing silver halideemulsion layer. From the standpoint of accelerating the colordevelopment, promoting the desilvering and reducing the residual colordue to sensitizing dyes, the yellow coupler-containing silver halideemulsion layer is preferably provided at the position remotest from thesupport than other silver halide emulsion layers. In view of thereduction in the bleach-fixing discoloration, the cyancoupler-containing silver halide emulsion is preferably provided as amid layer of other silver halide emulsion layers and in view of thereduction in the light discoloration, the cyan coupler-containing silverhalide emulsion layer is preferably provided as a lowermost layer. Eachof the yellow, magenta and cyan color-forming layers may be composed oftwo or three layers. It is also preferred to provide a coupler layercontaining no silver halide emulsion in adjacency to a silver halideemulsion layer to form a color-forming layer as described, for example,in JP-A-4-75055, JP-A-9-114035, JP-A-10-246940 and U.S. Pat. No.5,576,159.

As for the silver halide emulsions, other materials (for example,additives) and photographic constituent layers (for example, layerarrangement), which can be used in the present invention, and theprocessing method and additives for the processing, which can be usedfor the processing of the light-sensitive material of the presentinvention, those described in JP-A-62-215272, JP-A-2-33144 andEP-A-0355660, particularly those described in EP-A-0355660, arepreferred. In addition, the silver halide color photographiclight-sensitive materials and the processing methods therefor describedin JP-A-5-34889, JP-A-4-359249, JP-A-4-313753, JP-A-4-270344,JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854, JP-A-1-158431,JP-A-2-90145, JP-A-3-194539, JP-A-2-93641 and EP-A-0520457 may also bepreferably used.

Particularly, as for the reflection-type support, silver halideemulsion, foreign metal ion species which are doped in a silver halidegrain, storage stabilizer and antifoggant for silver halide emulsion,chemical sensitization method (including sensitizer), spectralsensitization method (including spectral sensitizer), cyan, magenta andyellow couplers and emulsification-dispersion method therefor, dye imagepreservability improver (for example, staining inhibitor anddiscoloration inhibitor), dye (for colored layer), gelatin species,layer structure of light-sensitive material and coating pH oflight-sensitive material, those described in patents shown in Tables 1and 2 may be preferably applied to the present invention.

TABLES 1 AND 2 Element JP-A-7-104448 JP-A-7-77775 JP-A-7-301895Reflection-type column 7, line column 35, line column 5, line support 12to column 12, 43 to column 44, 40 to column 9, line 19 line 1 line 26Silver halide column 72, line column 44, line column 77, line emulsion29 to column 74, 36 to column 46, 48 to column 80, line 18 line 29 line28 Foreign metal column 74, lines column 46, line column 80, line ionspecies 19 to 44 30 to column 47, 29 to column 81, line 5 line 6 Storagecolumn 75, lines column 47, lines column 18, line stabilizer and 9 to 1820 to 29 11 to column 31, antifoggant line 37 Chemical column 74, linecolumn 47, lines column 81, lines sensitization 45 to column 75, 7 to 179 to 17 method line 6 (chemical sensitizer) Spectral column 75, linecolumn 47, line column 81, line sensitization 19 to column 76, 30 tocolumn 49, 21 to column 82, method line 45 line 6 line 48 (spectralsensitizer) Cyan coupler column 12, line column 62, lines column 88,line 20 to column 39, 50 to 16 49 to column 89, line 49 line 16 Yellowcoupler column 87, line column 63, lines column 89, lines 40 to column88, 17 to 30 17 to 30 line 3 Magenta column 88, lines column 63, linecolumn 31, line coupler 4 to 18 3 to column 64, 34 to column 77, line 11line 44 and column 88, lines 32 to 46 Emulsification- column 71, linecolumn 61, lines column 87, lines dispersion 3 to column 72, 36 to 49 35to 48 method of line 11 coupler Dye image column 39, line column 61,line column 87, line storability 50 to column 70, 50 to column 62, 49 tocolumn 88, improver line 9 line 49 line 48 (staining inhibitor)Discoloration column 70, line inhibitor 10 to column 71, line 2 Dye(colorant) column 77, line column 7, line column 9, line 42 to column78, 14 to column 19, 27 to column 18, line 41 line 42 and line 10 column50, line 3 to column 51, line 14 Gelatin species column 78, lines column51, lines column 83, lines 42 to 48 15 to 20 13 to 19 Layer structurecolumn 39, lines column 44, lines column 31, line of light- 11 to 26 2to 35 38 to column 32, sensitive line 33 material Coating pH of column72, lines light-sensitive 12 to 28 material Scan exposure column 76,lines column 49, line column 82, line 6 to column 77, 7 to column 50, 49to column 83, line 41 line 2 line 12 Preservative in column 88, linedeveloper 19 to column 89, line 22

In addition, the couplers described in JP-A-62-215272, page 91, rightupper column, line 4 to page 121, left upper column, line 6,JP-A-2-33144, page 3, right upper column, line 14 to page 18, left uppercolumn, last line and page 30 right upper column, line 6 to page 35,right lower column, line 11, and EP-A-0355660, page 4, lines 15 to 27,page 5, line 30 to page 28, last line, page 45, lines 29 to 31, and page47, line 23 to page 63, line 50 are also useful as the cyan, magenta andyellow couplers for use in the present invention.

Furthermore, the compounds represented by formulae (II) and (III) ofWO-98/33760 and formula (D) of JP-A-10-221825 may also be preferablyused in the present invention.

These are described in more detail below.

The cyan coupler which can be used in the present invention ispreferably a pyrrolotriazole-base coupler and preferred examples thereofinclude the couplers represented by formulae (I) and (II) ofJP-A-5-313324, the couplers represented by formula (I) of JP-A-6-347960and the couplers described in these patents.

Also, phenol-base and naphthol-base cyan couplers may be preferably usedand preferred examples thereof include the cyan couplers represented byformula (ADF) of JP-A-10-333297.

Other preferred examples of the cyan coupler include pyrroloazole-typecyan couplers described in European Patent 0488248 and EP-A-0491197,2,5-diacylaminophenol couplers described in U.S. Pat. No. 5,888,716,pyrazoloazole-type cyan couplers having an electron-withdrawing group ora hydrogen bond group at the 6-position described in U.S. Pat. Nos.4,873,183 and 4,916,051, and particularly pyrazoloazole-type cyancouplers having a carbamoyl group at the 6-position described inJP-A-8-171185, JP-A-8-311360 and JP-A-8-339060.

In addition, diphenylimidazole-base cyan couplers described inJP-A-2-33144, 3-hydroxypyridine-base cyan couplers described inEP-A-0333185 (in particular, a 2-equivalent coupler obtained by allowingCoupler (42) as a 4-equivalent coupler to have a chlorine-releasinggroup, and Couplers (6) and (9) described as specific examples arepreferred), cyclic active methylene-base cyan couplers described inJP-A-64-32260 (in particular, Couplers 3, 8 and 34 described as specificexamples are preferred), pyrrolopyrazole-type cyan couplers described inEP-A-0456226, and pyrroloimidazole-type cyan couplers described inEuropean Patent 0484909 may also be used.

The magenta coupler for use in the present invention may be a5-pyrazolone-base magenta coupler or a pyrazoloazole-base magentacoupler described in known publications shown in the Tables above. Amongthese, in view of hue, image stability and color formability,pyrazolotriazole couplers described in JP-A-61-65245, in which asecondary or tertiary alkyl group is directly bonded to the 2-, 3- or6-position of a pyrazolotriazole ring; pyrazoloazole couplers containinga sulfonamide group within the molecule described in JP-A-61-65246;pyrazoloazole couplers having an alkoxyphenylsulfamide ballast groupdescribed in JP-A-61-147254; and pyrazoloazole couplers having an alkoxygroup or an aryloxy group at the 6-position described in EP-A-226849 andEP-A-294785, are preferred.

In particular, the magenta coupler is preferably a pyrazoloazole couplerrepresented by formula (M-I) of JP-A-8-122984 and the contents in theparagraphs 0009 to 0026 of this patent can be applied to the presentinvention as it is and are incorporated as a part of the presentspecification.

In addition, pyrazoloazole couplers having a steric hindrance group atboth the 3-position and the 6-position described in European Patents854384 and 884640 may also be preferably used.

Examples of the yellow coupler which can be preferably used include, inaddition to the compounds shown in the Tables above, acylacetamide-typeyellow couplers having a 3- to 5-membered ring structure at an acylgroup described in EP-A-0447969, malondianilide-type yellow couplerhaving a ring structure described in EP-A-0482552, andacylacetamide-type yellow couplers having a dioxane structure describedin U.S. Pat. No. 5,118,599. Among these, preferred areacylacetamide-type yellow couplers where the acyl group is1-alkylcyclopropane-1-carbonyl group, and malondianilide-type yellowcouplers where one of the anilides forms an indoline ring. Thesecouplers can be used individually or in combination of two or morethereof.

The coupler for use in the present invention is preferably emulsifiedand dispersed in an aqueous solution of hydrophilic colloid afterimpregnating the coupler in a loadable latex polymer (for example, thepolymer described in U.S. Pat. No. 4,203,716) in the presence (orabsence) of a high-boiling point organic solvent shown in the Tablesabove or after dissolving the dye together with a water-insoluble andorganic solvent-soluble polymer.

Examples of the water-insoluble and organic solvent-soluble polymerwhich can be preferably used include homopolymers and copolymersdescribed in U.S. Pat. No. 4,857,449, columns 7 to 15, and InternationalPatent Publication WO88/00723, pages 12 to 30. In view of the dye imagestability, methacrylate-base and acrylamide-base polymers are preferred,and acrylamide-base polymer is more preferred.

In the present invention, known color mixing inhibitors can be used andamong these, the compounds described the following patents arepreferred.

Examples of the color mixing inhibitor which can be used include highmolecular weight redox compounds described in JP-A-333501, phenidone andhydrazine-based compounds described in WO98/33760 and U.S. Pat. No.4,923,787, and white couplers described in JP-A-5-249637, JP-A-10-282615and German Patent 19629142A1. In the case of elevating the pH of thedeveloper and thereby performing rapid development, the redox compoundsdescribed in German Patent 19618786A1, EP-A-839623, EP-A-842975, GermanPatent 19806846A1 and French Patent 2760460A1 are preferred.

In the present invention, a compound containing a triazine skeletonhaving a high molar absorption coefficient is preferably used as anultraviolet absorber and for example, the compounds described in thefollowing patents can be used.

The compounds described in JP-A-46-3335, JP-A-55-152776, JP-A-5-197074,JP-A-5-232630, JP-A-5-307232, JP-A-6-211813, JP-A-8-53427,JP-A-8-234364, JP-A-8-239368, JP-A-9-31067, JP-A-10-115898,JP-A-10-147577, JP-A-10-182621, German Patent 19739797A, EP-A-711804 andJapanese Published Unexamined International Application 8-501291 can beused.

Although gelatin is advantageously used as the binder or protectivecolloid for use in the light-sensitive material of the presentinvention, other hydrophilic colloid can be used by itself or incombination with gelatin. In a preferred gelatin, the content of heavymetal impurities such as iron, copper, zinc and manganese is preferably5 ppm or less, more preferably 3 ppm or less.

The amount of calcium contained in the light-sensitive material ispreferably 20 mg/m² or less, more preferably 10 mg/m² or less, mostpreferably 5 mg/m² or less.

In the present invention, microbicide/antifungal described inJP-A-63-271247 is preferably added so as to prevent various molds andbacteria from proliferating in a hydrophilic colloid layer and therebydeteriorating the image.

The coating pH of the light-sensitive material is preferably from 4.0 to7.0, more preferably from 4.0 to 6.5.

In the present invention, from the standpoint of improving the coatingstability of the light-sensitive material, preventing the generation ofelectrostatic charge, controlling the electrostatic charge amount andthe like, a surfactant may be added to the light-sensitive material. Thesurfactant includes an anionic surfactant, a cationic surfactant, abetaine surfactant and a nonionic surfactant and examples thereofinclude those described in JP-A-5-333492. The surfactant for use in thepresent invention is preferably a surfactant containing a fluorine atom,more preferably a fluorine atom-containing surfactant.

The amount of the surfactant added to the light-sensitive material isnot particularly limited but is generally from 1×10⁻⁵ to 1 g/m²,preferably from 1×10⁻⁴ to 1×10⁻¹ g/m², more preferably from 1×10⁻³ to1×10⁻² g/m².

The fluorine atom-containing surfactant may be used by itself or incombination with another conventionally known surfactant but ispreferably used in combination with another conventionally knownsurfactant.

The light-sensitive material of the present invention is used for theprinting system using a normal negative printer and additionally, issuitably used for the scan exposure system using a cathode ray tube(CRT). The CRT exposure apparatus is simple and compact as compared withapparatuses using a laser and therefore, costs low. Also, the control ofoptical axis and colors is facilitated.

The cathode ray tube used for the image exposure is a luminous elementof various types, which emits light in a required spectral region. Forexample, a red luminous element, a green luminous element and a blueluminous element are used individually or in combination of two or more.The spectral region is not limited to these red, green and blue regionsbut a phosphor which emits light in the yellow, orange, ultraviolet orinfrared region may also be used. In particular, a cathode ray tubeusing a mixture of these luminous elements to emit white light is oftenused.

In the case where the light-sensitive material has a plurality oflight-sensitive layers different in the spectral sensitivitydistribution and the cathode ray tube also has phosphors which emitlight in a plurality of spectral regions, multiple colors may be exposedat a time, namely, the light may be emitted from the tube surface afterimage signals of multiple colors are input to the cathode ray tube. Amethod of sequentially inputting the image signals every each color,sequentially emitting light of respective colors, and performing theexposure through a film which cuts colors other than those colors(sequential exposure) may also be employed. In general, the sequentialexposure is advantageous for attaining high image quality because a highresolution cathode ray tube can be used.

The light-sensitive material of the present invention is preferably usedfor digital scanning exposure system using monochromatic high-densitylight such as gas laser, light-emitting diode, semiconductor laser orsecond harmonic generating light source (SHG) comprising a combinationof a nonlinear optical crystal with a semiconductor laser or a solidstate laser using a semiconductor laser as an excitation light source.In order to make the system compact and inexpensive, a semiconductorlaser or a second harmonic generating light source (SHG) comprising acombination of a nonlinear optical crystal with a semiconductor laser ora solid state laser is preferably used. Particularly, in order to designa compact and inexpensive apparatus having a long life and highstability, a semiconductor laser is preferably used and at least one ofexposure light sources is preferably a semiconductor laser.

In the case of using this scanning exposure light source, the spectralsensitivity maximum wavelength of the light-sensitive material of thepresent invention can be freely set according to the wavelength of thescanning exposure light source used. In the case of an SHG light sourceobtained by combining a nonlinear optical crystal with a semiconductorlaser or a solid state laser using a semiconductor laser as anexcitation light source, the oscillation wavelength of the laser can behalved and therefore, blue light and green light are obtained. As aresult, the light-sensitive material can have a spectral sensitivitymaximum in normal three wavelength regions of blue, green and red.

The exposure time in this scanning exposure is defined as the time forexposing a picture element size with a picture element density of 400dpi and the exposure time is preferably 10⁻⁴ sec or less, morepreferably 10⁻⁶ sec or less.

The preferred scanning exposure system which can be applied to thepresent invention is described in detail in the patents set forth in theTables above.

In processing the light-sensitive material of the present invention, theprocessing materials and processing methods described in JP-A-2-207250,page 26, right lower column, line 1 to page 34, right upper column, line9, and in JP-A-4-97355, page 5, left upper column, line 17 to page 18,right lower column, line 20, may be preferably applied. For thepreservative used in this developer, the compounds described in thepatents shown in the Tables above may be preferably used.

The present invention is preferably applied also to a light-sensitivematerial having suitability for rapid processing.

The color development time means a time period from a light-sensitivematerial enters in a color developer until it enters in a bleach-fixingsolution in the subsequent processing step. For example, in the case ofprocessing in an automatic developing machine, the sum total of two timeperiods, namely, the time period where the light-sensitive material isimmersed in a color developer (so-called in-liquid time) and the timeperiod where the light-sensitive material is departed from the colordeveloper and transferred in air toward the bleach-fixing bath in thesubsequent step (so-called in-air time), is called a color developmenttime. In the same way, the bleach-fixing time means the time period fromthe light-sensitive material enters in a bleach-fixing solution until itenters in the subsequent water washing or stabilizing bath. Also, thewater washing or stabilization time means a time period where thelight-sensitive material enters in the water washing or stabilizingsolution and stays in the liquid (so-called in-liquid time) inpreparation for the drying step.

In the present invention, when a rapid processing is performed, thecolor development time is preferably 15 seconds or less, more preferablyfrom 6 to 12 seconds. Similarly, the bleach-fixing time is preferably 15seconds or less, more preferably from 6 to 12 seconds. The water washingor stabilization time is preferably 50 seconds or less, more preferablyfrom 6 to 25 seconds.

After the exposure, the light-sensitive material of the presentinvention may be developed by a wet system, for example, a conventionaldevelopment method using a developer containing an alkali agent and adeveloping agent is used or a development method where a developingagent is incorporated into the light-sensitive material and thedevelopment is performed using an activator solution such as alkalisolution containing no developing agent, or may also be developed by aheat development system using no processing solution. Particularly, theactivator method uses a processing solution not containing a developingagent and therefore, the processing solution is facilitated in thecontrol and handling. Furthermore, the load at the treatment of wastesolution is reduced and this is preferred also in view of environmentalconservation.

In the activator method, the developing agent or a precursor thereofincorporated into the light-sensitive material is preferably ahydrazine-type compound described, for example, in JP-A-8-234388,JP-A-9-152686, JP-A-9-152693, JP-A-9-211814 AND JP-A-9-160193.

Furthermore, a development method where the coated silver amount of thelight-sensitive material is reduced and a treatment for intensifying theimage (intensification treatment) using hydrogen peroxide is performed,is also preferably used. Particularly, use of this method for theactivator method is advantageous. More specifically, an image formationmethod using an activator solution containing hydrogen peroxide ispreferred and this is described in JP-A-8-297354 and JP-A-9-152695.

In the activator method, desilvering generally follows the processingwith an activator solution, however, in the method including the imageintensification treatment and using a light-sensitive material having alow silver amount, the desilvering can be omitted and a simple and easyprocess such as water washing or stabilization may be performed. In thecase of a system of reading image information from a light-sensitivematerial using a scanner or the like, a processing form capable ofdispensing with desilvering can be employed even when a light-sensitivematerial having a high silver amount, such as a light-sensitive materialfor photographing, is used.

For the processing with the activator solution, the desilvering solution(bleach/fixing solution) and the washing and stabilizing solution, knownprocessing materials and known processing methods may be used. Preferredexamples thereof include those described in Research Disclosure, Item36544 (September 1994), pages 536 to 541, and JP-A-8-234388.

In exposing the light-sensitive material of the present invention in aprinter, a band stop filter described in U.S. Pat. No. 4,880,726 ispreferably used, whereby light color mixing can be removed and colorreproducibility can be greatly improved.

In the present invention, copy restriction may be applied bypre-exposing a yellow microdot pattern in advance of imparting the imageinformation as described in EP-A-0789270 and EP-A-0789480.

The present invention is described in greater detail below by referringto the Examples.

EXAMPLE 1

(Preparation of Cubic Emulsion A)

In a 5% aqueous solution of lime-processed gelatin, 5.6 g of sodiumchloride was added and thereto 42.8 ml of 1N sulfuric acid and 1.1 ml ofN,N′-dimethylimidazolidine-2-thione (1% aqueous solution) were added. Tothe resulting aqueous solution, an aqueous solution containing 0.21 molof silver nitrate and an aqueous solution containing 0.21 mol of sodiumchloride were added and mixed at 61° C. with stirring (first addition).Subsequently, while keeping the temperature at 61° C., an aqueoussolution containing 1.27 mol of silver nitrate and an aqueous solutioncontaining 1.27 mol of sodium chloride were added and mixed withstirring (second addition). Furthermore, an aqueous solution containing0.21 mol of silver nitrate and an aqueous solution containing 0.21 molof sodium chloride were added and mixed with stirring (third addition).Subsequently, an aqueous solution containing 0.21 mol of silver nitrateand an aqueous solution containing 0.21 mol of sodium chloride wereadded and mixed with stirring (fourth addition). Furthermore, whilekeeping the temperature at 61° C., an aqueous solution containing 0.02mol of silver nitrate and an aqueous solution containing 0.02 mol ofsodium chloride were added and mixed with vigorous stirring (fifthaddition). Subsequently, an aqueous solution containing 0.11 mol ofsilver nitrate and an aqueous solution containing 0.11 mol of sodiumchloride were added and mixed with stirring (sixth addition). Then, anaqueous solution containing 0.04 mol of silver nitrate and an aqueoussolution containing 0.04 mol of sodium chloride were added and mixedwith stirring (seventh addition. Finally, an aqueous solution containing0.04 mol of silver nitrate and an aqueous solution containing 0.04 molof sodium chloride were added and mixed at 61° C. with stirring (eighthaddition).

The resulting emulsion was desalted through precipitation and waterwashing at 40° C. and then, the pH and the pAg of the emulsion wereadjusted to 7.3 and 5.6, respectively, by adding 168.0 g oflime-processed gelatin. From an electron microphotograph, the grainshape was cubic, the grain size was 0.62 μm and the coefficient ofvariation in the grain size was 10%.

(Preparation of Cubic Emulsion B Containing Iodide and HexacyanoComplex)

Emulsion B was prepared in the same manner as Emulsion A except thatthese emulsions were different in the following points.

The halogen solution in the second addition contained 1.27 mol of sodiumchloride and a transition metal complex of K₂[Ru(NO)Cl₅] in an amount ofgiving a coverage of 1×10⁻⁸ mol/mol-Ag at the completion of grainformation.

The halogen solution in the fourth addition contained 0.21 mol of sodiumchloride and a transition metal complex of K₄[Ru(CN)₆] in an amount ofgiving a coverage of 2×10⁻⁵ mol/mol-Ag at the completion of grainformation.

The halogen solution in the fifth addition contained 0.02 mol of sodiumchloride and 0.005 mol of potassium iodide.

The halogen solution in the sixth addition contained 0.11 mol of sodiumchloride and a transition metal complex of K₂[Ir(H₂O)Cl₅] in an amountof giving a coverage of 2×10⁻⁸ mol/mol-Ag at the completion of grainformation.

The halogen solution in the seventh addition contained 0.04 mol ofsodium chloride and a transition metal complex of K₂[IrCl₆] in an amountof giving a coverage of 4×10⁻⁸ mol/mol-Ag at the completion of grainformation.

From the electron microphotograph, the shape of obtained grains wascubic, the grain size was 0.62 μm and the coefficient of variation inthe grain size was 10%.

(Chemical Sensitization and Spectral Sensitization)

To each of Emulsions A and B, a gold sensitizer(bis(1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) Au(I)tetrafluoroborate), a sulfur sensitizer (sodium thiosulfate) and3.8×10⁻⁴ mol/mol-Ag of a spectral sensitizing dye shown in Table 3 wereadded to optimally perform the chemical sensitization and spectralsensitization at 60° C. Furthermore, 4.4×10⁻⁴ mol/mol-Ag of1-(5-methylureidophenyl)-5-mercaptotetrazole was added.

Sensitizing Dye A

Sensitizing Dye B

(Preparation of Coated Sample)

On the surface of a support obtained by coating both surfaces of paperwith polyethylene resin, a corona discharge treatment was applied.Thereafter, a gelatin undercoat layer containing sodiumdodecylbenzenesulfonate was provided and furthermore, the fist toseventh photographic constituent layers were provided in sequence toprepare silver halide color photographic light-sensitive materialSamples (T101) to (T112) having the following layer structure. Thecosting solution for each photographic constituent layer was prepared asfollows.

Preparation of Coating Solution

Couplers, Dye image stabilizers and ultraviolet absorbers were dissolvedin a solvent and ethyl acetate, the obtained solution wasemulsification-dispersed in an aqueous 10 wt % gelatin solutioncontaining a surfactant by means of a high-speed stirring emulsifier(dissolver), and water was added thereto to prepare an emulsifieddispersion.

The thus-obtained emulsified dispersion and a high chloride emulsionwere mixed and dissolved to prepare a coating solution having acomposition shown later.

In each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as agelatin hardening agent. Furthermore, in each layer, Ab-1, Ab-2 and Ab-3shown below were added to give a total amount of 15.0 mg/m², 60.0 mg/m²and 5.0 mg/m², respectively.

Antiseptic (Ab-1)

Antiseptic (Ab-2)

Antiseptic (Ab-3)

The high silver chloride emulsion used in each light-sensitive emulsionlayer was as follows.

Blue-sensitive Emulsion Layer

An emulsion shown in Table 3 was used.

Green-sensitive Emulsion Layer

Sensitizing Dye C was added to a silver chlorobromide emulsion (cubic; a1:3 (by mol of silver) mixture of a large-size emulsion having anaverage grain size of 0.45 μm and a small-size emulsion having anaverage grain size of 0.35 μm, with the coefficient of variation in thegrain size being 10% and 8%, respectively; the emulsion of each sizecontaining 0.4 mol % of silver bromide localized on a part of thesurface of a grain comprising a silver chloride substrate) in an amountof 3.0×10⁻⁴ mol for the large-size emulsion and in an amount of 3.6×10⁻⁴mol for the small-size emulsion, per mol of silver halide. Furthermore,Sensitizing Dye D was added in an amount of 4.0×10⁻⁵ mol for thelarge-size emulsion and in an amount of 2.8×10⁻⁴ mol for the small-sizeemulsion, per mol of silver halide.

(Sensitizing Dye C)

(Sensitizing Dye D)

Red-sensitive Emulsion Layer

Sensitizing Dyes E and F were added to a silver chlorobromide emulsion(cubic; a 1:4 (by mol of silver) mixture of Large-Size Emulsion A havingan average grain size of 0.50 μm and Small-Size Emulsion B having anaverage grain size of 0.41 μm, with the coefficient of variation in thegrain size being 0.09 and 0.11, respectively; the emulsion of each sizecontaining 0.8 mol % of silver bromide localized on a part of thesurface of a grain comprising a silver chloride substrate) each in anamount of 6.0×10⁻⁵ mol for the large-size emulsion and each in an amountof 9.0×10⁻⁵ mol for the small-size emulsion, per mol of silver halide.

(Sensitizing Dye E)

(Sensitizing Dye F)

Furthermore, Compound I shown below was added in an amount of 2.6×10⁻³mol per mol of silver halide.

(Compound I)

To the blue-sensitive, green-sensitive and red-sensitive emulsionlayers, 1-(3-methylureidophenyl)-5-mercaptotetrazole was added in anamount of 3.3×10⁻⁴ mol, 1.0×10⁻³ mol and 5.9×10⁻⁴ mol, respectively, permol of silver halide.

To the second, fourth, sixth and seventh layers, the same compound wasadded to have a coverage of 0.2 mg/m², 0.2 mg/m², 0.6 mg/m² and 0.1mg/m², respectively.

Furthermore, to the red-sensitive emulsion layer, 0.05 g/m² of amethacrylic acid/butyl acrylate copolymer (weight ratio: 1:1, averagemolecular weight: 200,000 to 400,000) was added. Also, to the second,fourth and sixth layers, disodium catechol-3,5-disulfonate was added tohave a coverage of 6 mg/m², 6 mg/m² and 18 mg/m², respectively.

For the purpose of preventing irradiation, the following dyes (in theparenthesis, the coated amount is shown) were added to the emulsionlayers.

(Layer Structure)

The layer structure is shown below. The numeral shows the coated amount(g/m²). In the case of silver halide emulsions, the coated amount is acoated amount in terms of silver.

Support

Polyethylene resin laminated paper [polyethylene resin in the firstlayer side contained white pigments (TiO₂ to a content of 16 wt % andZnO to a content of 4 wt %), 13 mg/m² of a fluorescent whitening agent(i.e., a brightening agent) (4,4′-bis(5-methylbenzoxazolyl)stilbene) and96 mg/m² of a bluish dye (ultramarine)]

First Layer (Blue-sensitive Emulsion Layer)

Emulsion 0.24 Gelatin 1.25 Yellow Coupler (ExY) 0.57 Dye ImageStabilizer (Cpd-1) 0.07 Dye Image Stabilizer (Cpd-2) 0.04 Dye ImageStabilizer (Cpd-3) 0.07 Dye Image Stabilizer (Cpd-4) 0.02 Solvent(Solv-1) 0.21

Second Layer (Color Mixing Inhibiting Layer)

Gelatin 0.60 Color Mixing Inhibitor (Mid-1) 0.10 Color Mixing Inhibitor(Mid-2) 0.18 Color Mixing Inhibitor (Mid-3) 0.02 Ultraviolet Absorber(UV-C) 0.05 Solvent (Solv-5) 0.11

Third Layer (Green-sensitive Emulsion Layer)

Emulsion 0.14 Gelatin 0.73 Magenta Coupler (ExM) 0.15 Ultravioletabsorber (UV-A) 0.05 Dye Image Stabilizer (Cpd-2) 0.02 Color MixingInhibitor (Cpd-7) 0.008 Dye Image Stabilizer (Cpd-4) 0.08 Dye ImageStabilizer (Cpd-5) 0.02 Dye Image Stabilizer (Cpd-6) 0.009 Dye ImageStabilizer (Cpd-7) 0.0001 Solvent (Solv-3) 0.06 Solvent (Solv-4) 0.11Solvent (Solv-5) 0.06

Fourth Layer (Color Mixing Inhibiting Layer)

Gelatin 0.48 Color Mixing Inhibitor (Mid-4) 0.07 Color Mixing Inhibitor(Mid-2) 0.006 Color Mixing Inhibitor (Mid-3) 0.006 Ultraviolet absorber(UV-C) 0.04 Solvent (Solv-5) 0.09

Fifth Layer (Red-sensitive Emulsion Layer)

Emulsion 0.12 Gelatin 0.59 Cyan Coupler (ExC-1) 0.13 Cyan Coupler(ExC-2) 0.03 Color Mixing Inhibitor (Mid-3) 0.01 Dye Image Stabilizer(Cpd-5) 0.04 Dye Image Stabilizer (Cpd-8) 0.19 Dye Image Stabilizer(Cpd-9) 0.04 Solvent (Solv-5) 0.09

Sixth Layer (Ultraviolet Absorbing Layer)

Gelatin 0.32 Ultraviolet Absorber (UV-C) 0.42 Solvent (Solv-7) 0.08

Seventh Layer (Protective Layer)

Gelatin 0.70 Acryl-modified polymer of polyvinyl 0.04 alcohol(modification degree: 17%) Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01Polydimethylsiloxane 0.01 Silicon dioxide 0.003

Yellow Coupler (ExY)

A 70:30 (by mol) mixture of:

Magenta Coupler (ExM)

A 40:40:20 (by mol) mixture of

Cyan Coupler (ExC-1)

Cyan Coupler (ExC-2)

A 50:25:25 (by mol) mixture of

Dye Image Stabilizer (Cpd-1)

Number average molecular weight: 60,000

Dye Image Stabilizer (Cpd-2)

Dye Image Stabilizer (Cpd-3)

n: 7 to 8 (average)

Dye Image Stabilizer (Cpd-4)

Dye Image Stabilizer (Cpd-5)

Dye Image Stabilizer (Cpd-6)

Dye Image Stabilizer (Cpd-7)

Dye Image Stabilizer (Cpd-8)

Dye Image Stabilizer (Cpd-9)

Color Mixing Inhibitor (Mid-1)

Color Mixing Inhibitor (Mid-2)

Color Mixing Inhibitor (Mid-3)

Color Mixing Inhibitor (Mid-4)

Ultraviolet Absorber (UV-1)

Ultraviolet Absorber (UV-2)

Ultraviolet Absorber (UV-3)

Ultraviolet Absorber (UV-4)

Ultraviolet Absorber (UV-6)

Ultraviolet Absorber (UV-7)

(UV-A)

A 4/2/2/3 (by weight) mixture of UV-1/UV-2/UV-3/UV-4

(UV-C)

A 1/1/1/2 (by weight) mixture of UV-2/UV-3/UV-6/UV-7

Surface Active Agent (Cpd-13)

A 7:3 (by mol) mixture of

As such, coated Samples T101 to T112 were prepared.

(Pressure Fogging Test)

On each sample, a needle having a diameter of 0.1 mm under a load of 10g was moved at a speed of 600 mm/min (pressure treatment). Using asample developed without passing through exposure, the difference in thedensity (called “pressure fogging”) between the portion subjected to thepressure treatment and the portion not subjected to the pressuretreatment was measured by means of a microdensitometer having anaperture size of 10 μm.

(Exposure)

Using the following exposure apparatus, each sample was exposed to thegradation of three color separation by means of three color laser raysof B, G and R. At this time, the laser output was corrected to obtainoptimum improvements in each sample.

(Exposure Apparatus)

The light sources used were a YAG solid laser (oscillation wavelength:946 nm) using a semiconductor laser GaAlAs (oscillation wavelength:808.5 nm) as the excitation light source and being subjected to thewavelength conversion using SHG crystal of LiNbO₃ having an inverteddomain structure to take out 473 nm, a YVO₄ solid laser (oscillationwavelength: 1,064 nm) using a semiconductor laser GaAlAs (oscillationwavelength: 808.5 nm) as the excitation light source and being subjectedto the wavelength conversion using SHG crystal of LiNbO₃ having aninverted domain structure to take out 532 nm, and an AlGaInP laser(oscillation wavelength: 680 nm; Type No. LN9R20, manufactured byMatsushita Electric Industrial Co., Ltd.). Respective laser rays ofthree colors were modulated in the intensity by AOM and moved in thedirection perpendicular to the scanning direction using a polygon mirrorso as to sequentially scan and thereby expose a color photographicpaper. For preventing the semiconductor laser from fluctuating in thequantity of light due to temperature, the temperature was kept constantby utilizing a Peltier element. The scanning exposure was 600 dpi and bythe measurement using a light beam diameter measurement apparatus[1180GP, manufactured by Beam Scan Inc. (USA)], the B, G and R all werefound to have a beam diameter of 65 μm (a circular beam with thedifference between the diameter in the main scanning direction and thediameter in the sub-scanning direction being within 1%).

(Development Processing; Dry-to-dry Time of 70 seconds)

Each sample was subjected to color development processing using theprocessing solutions shown below through the following processing steps,however, exposure was not performed.

Tank Temperature Time Replenisher* Volume Processing Step (° C.) (sec)(ml) (liter) Color development 45 15 35 2 Bleach-fixing 40 15 38 1Rinsing (1) 40 10 — 1 Rinsing (2) 40 10 — 1 Rinsing (3) 40 10 90 1Drying 80 10 — — (A tank countercurrent system of Rinsing (3) → (1))*Replenishing amount per 1 m² of light-sensitive material.

In the above-described processing, the water of Rinsing (3) was sent bya pump to a reverse osmosis membrane. The penetrated water was fed torinsing (3) and the concentrated water not passed through the reverseosmosis membrane was fed back to rinsing (2) and used there. For savingthe crossover time, a blade was disposed between respective rinsingtanks and the sample was passed therethrough. In each step, acirculating processing solution was sprayed using a spraying apparatusdescribed in JP-A-8-314088 by setting the amount sprayed to 4 to 6liters/minute per one tank.

Each processing solution had the following composition.

Color Developer: Tank Solution Replenisher Water 700 ml 700 ml Sodiumtriisopropyl- 0.1 g 0.1 g naphathalene (β) sulfonateEthylenediaminetetraacetic 3.0 g 3.0 g acid Disodium 1,2-dihydroxy- 0.5g 0.5 g benzene-4,6-disulfonate Triethanolamine 12.0 g 12.0 gl Potassiumchloride 15.8 g — Potassium bromide 0.04 g — Potassium carbonate 27.0 g27.0 g Sodium sulfite 0.1 g 0.1 g Disodium N,N-bis(sulfonato- 18.0 g18.0 g ethyl)hydroxylamine N-Ethyl-N-(β-methanesulfon- 8.0 g 23.0 gamidoethyl)-3-methyl-4- aminoaniline sulfate Sodium bis(2,4-disulfonato-5.0 g 6.0 g ethyl-1,3,5-triazyl-6)- diaminostilbene-2,2- disulfonateWater to make 1,000 ml 1,000 ml pH (at 25° C.) 10.35 12.80

The bleach-fixing solution was prepared by mixing the followingtwo-component replenishers as follows.

Replenisher (38 ml/m² in total of the amounts Bleach-Fixing SolutionTank Solution shown below) First replenisher 260 ml 18 ml Secondreplenisher 290 ml 20 ml Water to make 1,000 ml pH (at 25° C.) 5.0

The first and second replenishers each had the following composition.

First Replenisher

Water 150 ml Ethylenebisguanidine nitrate 30 g Ammonium sulfitemonohydrate 226 g Ethylenediaminetetraacetic acid 7.5 gTriazinylaminostilbene-base fluorescent 1.0 g brightening agent (HakkolFWA-SF, produced by Showa Kagaku K.K.) Ammonium bromide 30 g Ammoniumthiosulfate (700 g/liter) 340 ml Water to make 1,000 ml pH (at 25° C.)5.82

Second Replenisher

Water 140 ml Ethylenediaminetetraacetic acid 11.0 g Ammoniumethylenediaminetetraacetato- 384 g ferrate (III) Acetic acid (50%) 230ml Water to make 1,000 ml pH (at 25° C.) 3.35

Rinsing Solution

Ion exchange water (with calcium and magnesium ion concentrations eachbeing 3 ppm or less)

The color formed samples after the completion of processing each wasmeasured on the reflection density using a TCD type density measuringapparatus manufactured by Fuji Photo Film Co., Ltd. The sensitivity isdetermined from the exposure amount necessary for giving a color density1.0 higher than the fogging density. The blue sensitivity was shown by arelative value assuming that the sensitivity of Sample 101 subjected to180-second processing was 100. The measurements results are showntogether with the results in the pressure fogging test in Table 3.

TABLE 3 Results of Blue Sensitivity, Fogging and Pressure Fogging CoatedSample 180-Second Processing 70-Second Processing No. Sensitizing BluePressure Blue Pressure (Emulsion No.) Dye Sensitivity Fogging FoggingSensitivity Fogging Fogging Remarks T101 (A) A 100 0.03 0.102 110 0.040.133 Comparison T102 (A) B 105 0.03 0.113 115 0.05 0.145 ComparisonT103 (A) I-12 120 0.02 0.080 125 0.03 0.125 Comparison T104 (A) I-13 1150.02 0.075 120 0.03 0.115 Comparison T105 (A) I-14 118 0.03 0.0098 1310.04 0.130 Comparison T106 (A) I-15 122 0.03 0.096 138 0.03 0.128Comparison T107 (B) A 215 0.05 0.142 225 0.06 0.188 Comparison T108 (B)B 225 0.05 0.150 230 0.06 0.192 Comparison T109 (B) I-12 238 0.03 0.120241 0.04 0.144 Invention T110 (B) I-13 230 0.03 0.115 242 0.04 0.145Invention T111 (B) I-14 240 0.03 0.120 250 0.03 0.140 Invention

It is seen from the results in Table 3 that the emulsions according tothe present invention succeeded in achieving high sensitivity by virtueof the introduction of iodide and hexacyano complex, nevertheless, werereduced in the fogging. In particular, the increase in fog densitygenerated on performing a rapid processing was small and a low fogdensity was ensured. The emulsions of the present invention showed thesame tendency also for the pressure fogging. That is, high sensitivitywas achieved by the introduction of iodide and hexacyano complex and atthe same time, the pressure fogging was low. In particular, the increasein pressure fog density generated on performing a rapid processing wasvery small.

EXAMPLE 2

(Preparation of Emulsion C Containing {100} Tabular Grains)

In a reactor, 1,200 ml of H₂O, 25 g of gelatin (deionized alkali-treatedgelatin having a methionine content of about 40 μmol/g), 0.4 g of sodiumchloride and 4.5 ml of a nitric acid 1N solution (having a pH of 4.5)were charged and the temperature was kept at 40° C. Then, Solution Ag-1(silver nitrate: 0.2 g/ml) and Solution X-1 (sodium chloride: 0.069g/ml) were added and mixed at 48 ml/min over 4 minutes while vigorouslystirring. After 15 seconds, 150 ml of an aqueous polyvinyl alcoholsolution [average polymerization degree of vinyl acetate: 1,700,containing 6.7 g of polyvinyl alcohol having an average saponificationratio to alcohol of 98% or more (hereinafter referred to as “PVA-1”), in1 liter of H₂O]was added.

Furthermore, 12.3 ml of a nitric acid 1N solution was added to adjustthe pH to 3.5. The temperature was elevated to 75° C. over 15 minutes,23 ml of a sodium hydroxide 1N solution was added to adjust the pH to6.5, and 4.0 ml of 1-(5-methylureidophenyl)-5-mercaptotetrazole (0.05%)and 4.0 ml of N,N′-dimethylimidazolidine-2-thione (1% aqueous solution)were added. Thereafter, 4 g of sodium chloride was added, the silverpotential (to saturated calomel electrode at room temperature) wasadjusted to 100 mV and then, as a growing process, Solution Ag-1 andSolution X-2 (containing 0.069 g/ml of sodium chloride and 3×10⁻¹⁰mol/ml of K[IrCl₅(H₂O)]) were simultaneously added for 17 minutes whilelinearly increasing the flow rate from 40 ml/min to 42 ml/min and whilekeeping the silver potential at 100 mV. Thereafter, 12.5 ml of a nitricacid 1N solution was added to adjust the pH to 4.0. Furthermore, 28.8 gof sodium chloride was added, the silver potential was adjusted to 60 mVand then, Solution Ag-2 (silver nitrate: 0.1 g/ml) and Solution X-3(sodium chloride: 0.0345 g/ml, KI: 3.8 mg/ml, K₄[Ru(CN)₆]: 2×10⁻⁷mol/ml) were added at a flow rate of 40 ml/min for 5 minutes. Theresulting emulsion was left standing at 75° C. for 10 minutes.

Thereafter, the emulsion was desalted through precipitation and waterwashing at 40° C. Thereto, 100 g of gelatin was added and the emulsionwas redispersed, thereby adjusting the pH and the pAg to 6.0 and 7.3,respectively. A part of the emulsion was sampled and an electronmicrophotograph image (TEM image) of the replica of grains was observed.As a result, it was found that 90% of the total projected area of allAgX grains were a tabular grain having {100} main plane and the tabulargrains had an average grain size of 0.80 μm, an average grain thicknessof 0.10 μm, and average aspect ratio of 7.8 and an average adjacentsides ratio of 1.2.

(Chemical Sensitization and Spectral Sensitization)

To Emulsion C, a gold sensitizer(bis(1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) Au(I)tetrafluoroborate), a sulfur sensitizer (sodium thiosulfate) and6.0×10⁻⁴ mol/mol-Ag of a spectral sensitizing dye shown in Table 4 tooptimally perform the chemical sensitization and spectral sensitizationat 60° C. Furthermore, 4.4×10⁻⁴ mol/mol-Ag of1-(5-methylureidophenyl)-5-mercaptotetrazole was added.

Coated Samples T201 and T202 were obtained in the same manner as CoatedSample T110 in Example 1 except for using Emulsion C as thegreen-sensitive emulsion. These samples were measured on thesensitivity, fogging and pressure fogging in the same manner as inExample 1. The results obtained are shown in Table 4.

TABLE 4 Coated Sample 180-Second Processing 70-Second Processing No.Sensitizing Blue Pressure Blue Pressure (Emulsion No.) Dye SensitivityFogging Fogging Sensitivity Fogging Fogging Remarks T201 (C) C 100 0.040.163 110 0.06 0.199 Comparison T202 (C) I-30 115 0.03 0.130 122 0.040.145 Invention

The sensitivity was shown by a relative value assuming that thesensitivity of Sample T201 was 100. As seen from Table 4, even with useof {100} tabular grains, when a dye according to the present inventionwas used, the sensitivity was high and the fogging and the pressurefogging were low.

By virtue of the construction in claim 1 of the present invention, alight-sensitive material having high sensitivity and reduced in thefogging (relatively low also in the pressure fogging) can be obtained.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide photographic light-sensitivematerial comprising at least one silver halide emulsion layer, whereinthe silver halide grain contained in said emulsion layer is silverchloroiodide or silver chloroiodobromide having a silver chloridecontent of 90 mol % or more and a silver iodide content of 0.01 to 1.0mol %, at least one hexacyano complex is doped in an amount of at least1×10⁻⁷ mol % based on the total silver amount, and said emulsion layercontains a methine dye represented by the following formula (I):

wherein Y represents an atomic group necessary for forming aheterocyclic ring or an atomic group necessary for forming a benzenering condensed with a heterocyclic ring, which may further be condensedwith another carbon ring or heterocyclic ring or may have a substituent,Z¹ and Z² each represents a single bond or an atomic group necessary forforming a nitrogen-containing heterocyclic ring which may further becondensed with another carbon ring or heterocyclic ring or may have asubstituent, R represents an alkyl group, an aryl group or aheterocyclic group, D represents a group necessary for forming a methinedye, L¹ and L² each represents a methine group, p represents 0 or 1, Mrepresents a counter ion, and m represents a number of 0 or morenecessary for neutralizing the electric charge within the molecule. 2.The silver halide photographic light-sensitive material as claimed inclaim 1, wherein in formula (I), Y represents an atomic group necessaryfor forming a pyrrole ring, a furan ring, a thiophene ring or a benzenering condensed with a pyrrole ring, a furan ring or a thiophene ring,and the ring formed by Y may be condensed with another carbon ring orheterocyclic ring or may have a substituent.
 3. The silver halidephotographic light-sensitive material as claimed in claim 1, wherein theformula (I) is selected from the following formula (II):

wherein Y¹¹ represents an atomic group necessary for forming a pyrrolering, a furan ring or a thiophene ring, or an atomic group necessary forforming an indole ring, a benzofuran ring or a benzothiophene ring,which may further be condensed with another carbon ring or heterocyclicring or may have a substituent, X¹¹ represents an oxygen atom, a sulfuratom, a selenium atom or NR¹³, R¹¹, R¹² and R¹³ each represents an alkylgroup, an aryl group or a heterocyclic group, Z¹¹ represents an atomicgroup necessary for forming a nitrogen-containing heterocyclic ringwhich may further be condensed with another carbon ring or heterocyclicring or may have a substituent, L¹¹, L¹², L¹³, L¹⁴ and L¹⁵ eachrepresents a methine group, p1 represents 0 or 1, n1 represents 0, 1, 2,3 or 4, M¹ represents a counter ion and m1 represents a number of 0 ormore necessary for neutralizing the electric charge within the molecule.4. The silver halide photographic light-sensitive material as claimed inclaim 1, wherein the formula (I) is selected from the following formula(III):

wherein Y²¹ represents an atomic group necessary for forming a pyrrolering, a furan ring or a thiophene ring, which may further be condensedwith another carbon ring or heterocyclic ring or may have a substituent,X²¹ and X²² each represents an oxygen atom, a sulfur atom, a seleniumatom or NR²³, R²¹, R²² and R²³ each represents an alkyl group, an arylgroup or a heterocyclic group, V²¹, V²², V²³ and V²⁴ each represents ahydrogen atom or a substituent, provided that two adjacent substituentsare not combined with each other to form a saturated or unsaturatedcondensed ring, L²¹, L²² and L²³ each represents a methine group, n2represents 0, 1, 2, 3 or 4, M² represents a counter ion and m2represents a number of 0 or more necessary for neutralizing the electriccharge within the molecule.
 5. The silver halide photographiclight-sensitive material as claimed in claim 1, wherein the silverhalide grain is doped with at least one Ir complex.
 6. The silver halidelight-sensitive material as claimed in claim 1, wherein silver halidegrains occupying 50% or more of the entire grain volume have a highsilver bromide localized phase having a silver bromide content 10 mol %or more higher than that of the adjacent phase and said high silverbromide localized phase contains at least one Ir complex.
 7. A methodfor forming an image, comprising imagewise exposing and developing asilver halide photographic light-sensitive material comprising a supporthaving thereon at least one silver halide emulsion layer, wherein saidsilver halide light-sensitive material is the light-sensitive materialclaimed in claim 1 and the total processing time of said light-sensitivematerial is 75 seconds or less.
 8. The method for forming an image asclaimed in claim 7, wherein digital scanning exposure is performed. 9.The silver halide photographic light-sensitive material as claimed inclaim 1, wherein in formula (I), Y represents an atomic group necessaryfor forming a heterocyclic ring or an atomic group necessary for formingan indole ring or a benzofuran ring.